CN102911381A - 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, can absorb large quantity of moisture and swelling in water, and can continue to keep its original structure after swelling and not dissolved.Because of 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 present main gel process for preparing that the method for employing chemosynthesis prepares high-molecular gel.
Chemically crosslinked type hydrogel is to use prior synthesizing method or the technology such as radiation, photopolymerization, the covalent cross-linking network that forms by copolymerization or polycondensation.In cross-linked phase, hydrogel reaches certain equilibrium swelling degree according to different cross-linking densities, therefore form cluster structure in the crosslinked low swelling of height zone, they are dispersed in the high swelling of the low cross-linking zone, cause the aggregate of high crosslink density because hydrophobicity is assembled, thereby caused the unhomogeneity of hydrogel structure.Chemical cross-linking agent commonly used comprises glutaraldehyde, formaldehyde, epoxy chloropropane, diacetyl oxide, diglycidyl ether, hot 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 the water; Described nanoparticle has an amphipathic segmented copolymer by what polyoxyethylene glycol/polyester formed, introduces crosslinkable groups at two ends, press finite concentration water-soluble, the spontaneous micella that is assembled into, and initiated polymerization is cross-linked to form behind the adding initiator.Chinese patent CN100390220C discloses a kind of method for preparing hydrogel, the method comprises: be dissolved in after vinyl monomer, linking agent and initiator are mixed and make reaction system in the solvent, the weight ratio of each composition is in this reaction system: monomer: linking agent: initiator: solvent=100: 2-50: 0.2-1: 1-10.Utilize frequency for microwave or the 300MHz-300GHz variable frequency microwave of 2450MHz reaction system to be carried out obtaining after the irradiated heat.
Physical crosslinking type gel refers to the network structure that polymer chain forms by different interactions such as molecular entanglement and ion, hydrogen bond, hydrophobic association and electrostatic interaction etc.Chinese patent CN200810036457.2 discloses a kind of composite aquogel and preparation method with high clay content of critical solution temperature.The 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 the trisodium phosphate modification.Hectorite mainly plays the effect of physical crosslinking agent.
Formed physical crosslinking type hydrogel is called again ionomer hydrogel (Ionotropic Hydrogel) during the polyvalent ion bonding of polyelectrolyte and oppositely charged.Group with the both positive and negative electric charge is arranged on the ionomer polyampholyte hydrogel, between positive and negative charge, formed ionomer.Ionic cross-linked bond is compared with covalent linkage, belongs to weak interaction, and is more responsive to environmental evolution.For example, the ion crosslinking agent that is used for chitosan is multivalent anions normally, such as SO
4 2-, tripoly phosphate sodium STPP, Trisodium Citrate etc.; The ion crosslinking agent that is used for sodium alginate is polyvalent cation, such as Ca
2+, Zn
2+Deng.Even sodium alginate aqueous solution under room temperature and physiological pH value, runs into divalence (except the magnesium ion), polyvalent metal ion, gelation reaction will occur, form the alginate hydrogel of ionomer.It has been generally acknowledged that calcium ion combines with guluronic acid residues in the sodium alginate molecule, calcium ion is among the encirclement of carboxylate radical negative ion, just as the egg in the egg box, thereby often is called as " egg box " model.Chinese patent CN102086592B discloses polyalcohol hydrogel of a kind of ionomer grafting on fiber and preparation method thereof.The preparation method is: with uv-radiation grafted polyacrylic acid on fiber, with in the 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 scrape off adhesion, put it in the calcium chloride water crosslinkedly, obtain the alginate calcium hydrogel of grafting on fiber.
Can be found out by upper analysis, at present gel crosslinked mainly with unicity crosslinked be main, document or the patent of the composite preparation gel of different sorts linking agent are also considerably less.Considerable change all occurs in swelling behavior, bore hole size, mechanical property and the respondent behavior of composite gel after crosslinked.The present invention has considered characteristics and the character of chemistry, physics and ion crosslinking agent, adopt different composite linking agents for different function monomers, overcome that the single crosslinked gel swelling that causes is low, poor mechanical property and the uneven first-class shortcoming of network structure, realization is to the composite crosslinking of molecular chain, form multiple cross-linked network, effectively regulate swelling capacity, hole form and the physical strength of high-molecular gel, constantly near 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 the crosslinked different properties monomer of chemistry, ion and physical crosslinking agent, rationally regulate composition and engineering condition, parameter etc., different service requirementss and different gel are satisfied in preparation, and have 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 monomer concentration, feed ratio, linking agent kind and the adjustings such as consumption, crosslinker compounding type, temperature of reaction, water content and order of addition(of ingredients).
The present invention realizes by following technical scheme.
A kind of chemistry/ion/physical compounding cross-linked hydrogel is 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 the glutaraldehyde.
Described polyvalent ion biopolymer M3 is the mixture of a kind of or any two kinds of compositions in sodium alginate, chitosan, the 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 the zinc sulfate.
Described physical crosslinking agent M5 is any one in magnesium hectorite, hectorite, magnesium soap stone, sauconite or the lithium magnesium silicate, outward appearance is the white solid powder, but in water after stirring Uniform Dispersion, in water, peel off fully, its lamella diameter 25-30nm, thickness is 0.9-1nm, and sheet surfaces is with a large amount of negative charges, and the edge is with negative charge.
The preparation method of a kind of chemistry/ion of the present invention/physical compounding cross-linked hydrogel comprises the steps:
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: add successively physical crosslinking agent M5, olefin monomer M1 and chemical cross-linking agent M2 in the deionized water, be mixed with the aqueous solution that mass concentration is 8-15%, whenever 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 the magnetic agitation, polyvalent ion biopolymer M3 is slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately ion crosslinking agent M4 and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately initiator ammonium persulfate or Potassium Persulphate, catalyzer Tetramethyl Ethylene Diamine or S-WAT, behind the 5min mixing solutions is slowly poured in the glass mold that thickness is 1～5mm, the 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 the 50mL deionized water, place 2～6 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
The mass percent of M1 in step 1 of the present invention～3: 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 the 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, in membranaceous or spherical any one.
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 regulated 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).
Described chemistry/ion/physics composite crosslinking gel is at least a in chemistry/ion composite crosslinking gel, ion/physics composite crosslinking gel, chemical/physical composite crosslinking gel or the chemistry/ion/physics composite crosslinking gel.
Adopt the application of the chemistry/ion of aforesaid method preparation/physics composite crosslinking gel 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 the physical crosslinking effect, physical crosslinking agent M5 lamella and initiator interact and attract in the M5 sheet surfaces, and initiated polymerization, one end of the molecular chain that the M1 polymerization forms is fixed on the M5 sheet surfaces, chainpropagation is continued in the active centre of the other end, then carry out chain termination with multi-form, finally form physical cross-linked network.With regard to the ionomer effect, polyvalent ion biopolymer M3 such as sodium alginate are comprised of D-MANNOSE aldehydic acid and 2 kinds of uronic acids of L-guluronic acid, and wherein multivalent metal cation is (such as Ca
2+) can displace the Na of L-guluronic acid combination
+, and the water-insoluble gel of formation egg case structure.The chemically crosslinked effect is the most traditional crosslinking method, repeats no more here.
Compare with the preparation method with existing gel, the present invention has the following advantages:
1. the composite crosslinking hydrogel of the present invention preparation 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 is crosslinked or the poor shortcoming of physical/chemical composite crosslinking gel comprehensive mechanical property.
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, can prepare on original synthesis device.
3. according to polymerization mechanism, the present invention can be by regulating linking agent kind and composite than waiting chemistry/ion of obtaining different swelling capacity, responsiveness, bore hole size, dye uptake and mechanical property/physical compounding cross-linked hydrogel.
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.
Description of drawings
Fig. 1 is the height stretching hydrogel of composite crosslinking preparation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should understand; these embodiment only are not used in for explanation the present invention and limit the scope of the invention; other any do not run counter to change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read 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: add successively 0.001g hectorite, 1g acrylamide and 0.001g methylene-bisacrylamide in the deionized water, be mixed with mass concentration and be 10% the aqueous solution, whenever 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 the magnetic agitation, the 0.1g sodium alginate is slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately 0.01g calcium sulfate and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately 0.1g initiator ammonium persulfate, 0.003g catalyzer Tetramethyl Ethylene Diamine, behind the 5min mixing solutions is slowly poured in the bar-shaped glass mold that thickness is 2mm, the control 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 the 50mL deionized water, place 4 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
Gained chemistry/ion/physics composite crosslinking gel is fully transparent, can be stretched as 12 times of former length, and can reply fully, can be used for foodstuffs industry.
Embodiment 2
1) preparation of chemically crosslinked gel pre-polymerization liquid: add successively 2g N-isopropylacrylamide and 0.002g methylene-bisacrylamide in the deionized water, be mixed with mass concentration and be 9% the aqueous solution, whenever 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 the magnetic agitation, 0.1g sodium alginate and 0.05g chitosan are slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately 0.02g calcium sulfate and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately 0.2g initiator potassium persulfate, 0.006g catalyzer S-WAT, behind the 5min mixing solutions is slowly poured in the column glass mold that thickness is 1mm, the control 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 the 50mL deionized water, place 3 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
Gained chemistry/ion composite crosslinking gel is fully transparent, can be stretched as 10 times of former length, and can reply fully, can be used for organizational project.
Embodiment 3
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: add successively 0.002g lithium magnesium silicate, 1g n-methylolacrylamide and 0.01g glutaraldehyde in the deionized water, be mixed with mass concentration and be 11% the aqueous solution, whenever 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 the magnetic agitation, 0.05g sodium alginate and 0.05g polylysine are slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately 0.005 calcium phosphate and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately 0.1g initiator potassium persulfate, 0.003g catalyzer Tetramethyl Ethylene Diamine, behind the 5min mixing solutions is slowly poured in the hollow form glass mold that thickness is 5mm, the control 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 the 50mL deionized water, place 5 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
Gained chemistry/ion/physics composite crosslinking gel is fully transparent, can be stretched as 7 times of former length, and can reply fully, can be used for agricultural irrigation.
Embodiment 4
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: add successively 0.0005g magnesium hectorite, 3g sodium acrylate and 0.004g diglycidyl ether in the deionized water, be mixed with the aqueous solution that mass concentration is 13wt%, whenever 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 the magnetic agitation, 0.25g sodium alginate and 0.05g chitosan are slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately 0.02g calcium chloride and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately 0.3g initiator potassium persulfate, 0.009g catalyzer S-WAT, behind the 5min mixing solutions is slowly poured in the globular glass mould that thickness is 4mm, the control 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 the 50mL deionized water, place 5 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
Gained chemistry/ion/physics composite crosslinking gel is fully transparent, can be stretched as 6 times of former length, and can reply fully, can be used for dye adsorption.
Embodiment 5
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: add successively 0.001g sauconite, 2g 2-(dimethylamino) ethyl-Methacrylamide and 0.002g two (methyl) vinylformic acid glycol ester in the deionized water, be mixed with the aqueous solution that mass concentration is 10wt%, whenever 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 the magnetic agitation, the 0.2g sodium alginate is slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately the mixture of 0.04g calcium carbonate and zinc chloride and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately 0.2g initiator ammonium persulfate, 0.006g catalyzer Tetramethyl Ethylene Diamine, behind the 5min mixing solutions is slowly poured in the glass mold that thickness is 3mm, the control 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 the 50mL deionized water, place 3 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
Gained chemistry/ion/physics composite crosslinking gel is fully transparent, and can be stretched as 5 times of former length, and can reply fully, be porous spongy after the lyophilize, can be used for biological medicine.
Claims (9)
1. chemistry/ion/physical compounding cross-linked hydrogel, it 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, its inorganic salt, with and composition thereof, described chemical cross-linking agent M2 is N, N '-methylene-bisacrylamide, two (methyl) vinylformic acid glycol ester, the diglycidyl ether, in epoxy chloropropane and the glutaraldehyde any one.Described polyvalent ion biopolymer M3 is sodium alginate, chitosan, the mixture of a kind of or any two kinds of compositions in the 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 the zinc sulfate, described physical crosslinking agent M5 is the magnesium hectorite, hectorite, magnesium soap stone, in sauconite or the lithium magnesium silicate any one, outward appearance is the white solid powder, but in water after stirring Uniform Dispersion, in water, peel off fully, its lamella diameter 25-30nm, thickness is 0.9-1nm, sheet surfaces is with a large amount of negative charges, and the edge is with negative charge.
2. the preparation method of a kind of chemistry/ion according to claim 1/physical compounding cross-linked hydrogel comprises the following steps:
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: add successively physical crosslinking agent M5, olefin monomer M1 and chemical cross-linking agent M2 in the deionized water, be mixed with the aqueous solution that mass concentration is 8-15%, whenever 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 the magnetic agitation, polyvalent ion biopolymer M3 is slowly added in the pre-polymerization liquid in the step 1, after occurring without aggregate, add immediately ion crosslinking agent M4 and mass concentration and be 0.1% softening agent glycerine, 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 when beginning to occur, add immediately initiator ammonium persulfate or Potassium Persulphate, catalyzer Tetramethyl Ethylene Diamine or S-WAT, behind the 5min mixing solutions is slowly poured in the glass mold that thickness is 1～5mm, the 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 the 50mL deionized water, place 2～6 ℃ of refrigerators to carry out swelling, be placed on lyophilize in-60 ℃ of cryogenic refrigerators 1 week, namely obtain the composite crosslinking gel solid of described drying, kept dry is for subsequent use.
3. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel, the mass percent that it is characterized in that M1 in step 1 of the present invention～3: M2: M3: M4: M5 is: M1: 82-97%, M2: 0-1%, M3: 3-15%, M4: 0-2%, M5: 0-2 ‰.
4. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel is characterized in that described polyreaction is any one in original position radical polymerization, microwave radiation, uv photopolymerization or the atom transfer radical polymerization.
5. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel, 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, in membranaceous or spherical any one.
6. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel is characterized in that described initiator and catalyzer are 1% and 3 ‰ of olefin monomer M1 consumptions.
7. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel, 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 regulated 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).
8. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel is characterized in that described chemistry/ion/physics composite crosslinking gel comprises in chemistry/ion composite crosslinking gel, ion/physics composite crosslinking gel, chemical/physical composite crosslinking gel or the chemistry/ion/physics composite crosslinking gel at least a.
9. the preparation method of a kind of chemistry/ion according to claim 2/physical compounding cross-linked hydrogel is characterized in that the application of chemistry/ion/physics composite crosslinking gel in organizational project, foodstuffs industry, agricultural irrigation, daily-use chemical industry, oil production, dye adsorption and biomedicine field.
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