CN105085791A - Preparation method of hydrophobic microsphere toughened and reinforced physical crosslinking double-network hydrogel - Google Patents
Preparation method of hydrophobic microsphere toughened and reinforced physical crosslinking double-network hydrogel Download PDFInfo
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Abstract
The invention provides a preparation method of hydrophobic microsphere toughened and reinforced physical crosslinking double-network hydrogel. The hydrophobic microsphere toughened and reinforced physical crosslinking double-network hydrogel consists of a first network and a second network by interpenetration, wherein the first network has a double-helix structure formed by gelatin macromolecular chains by virtue of hydrogen bond interaction; and the second network is a micelle which takes hydrophobic microspheres as a center and is formed by hydrophobic monomers in a copolymer of a co-monomer II namely acrylamide and a hydrophobic monomer namely hexadecyl methacrylate under the action of an emulsifier. The hydrophobic monomers and the hydrophobic microspheres in the hydrogel have a relatively strong hydrophobic association action, so that the elongation at break of the hydrogel reaches up to 6000%, the tensile strength reaches up to 2MPa, the mechanical properties of the hydrogel are improved, and the application field of the hydrogel is broadened.
Description
Technical field
The invention belongs to synthesis and the activeness and quietness technology of hydrogel, relate to a kind of preparation method of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel.
Background technology
Hydrogel is the macromolecular material with three-dimensional netted crosslinking structure.Due to macromole mainly hydrophilic in molecular structure, so can a large amount of water be absorbed.Hydrogel properties is soft, is similar to vital tissues material, has good biocompatibility, be therefore widely used in organizational project, medicinal slow release agent, tissue stent material etc.But most of hydrogel needs the Application Areas of high-toughness high-strength hydrogel to be restricted because its mechanical property is poor at some, for example, tendon, cartilage etc.The scholar that China is a lot of is devoted to raising and the improvement of studying hydrogel mechanical property.Successively achieve macromole topology hydrogel, Nanometer composite hydrogel, double-network hydrogel, macromolecular microspheres cross-linked hydrogel, hydrophobic association hydrogel etc.And the research and development of China Water gel is more late, there are a certain distance in the state of the art of hydrogel material and application level and the developed country such as Japan, the U.S., hydrogel major part required for China is import, and therefore, the R and D of hydrogel are of great significance Chinese market tool.
Although traditional double-network hydrogel improves the mechanical property of hydrogel to a great extent, such as, in traditional chemically crosslinked double-network hydrogel, first network is strong electrolyte, drawing process Fracture is broken, fine grained chippings becomes second network stress branch and physical crosslinking point, the power energy performance deficiency of second network is reduced, the mechanical property of hydrogel increases, but can't meet the requirement to hydrogel mechanical property.In order to further improve the mechanical property of double-network hydrogel, research worker has achieved certain effect.(the ANovelDesignStrategyforFullyPhysicallyLinkedDoubleNetwor kHydrogelswithTough such as domestic Institutes Of Technology Of He'nan Chen Qiang, FatigueResistant, andSelf-HealingProperties, 2015) prepare physical crosslinking double-network hydrogel.Physical crosslinking double-network hydrogel is greatly improved compared with the toughness of chemically crosslinked aquagel and self-healing, and its elongation at break reaches more than 5260%, tensile strength 0.376MPa.(the Microgel-ReinforcedHydrogelFilmswithHighMechanicalStreng thandTheirVisibleMesoscaleFractureStructure such as Hokkaido, Japan university Gong Jian duckweed, Macromolecules, 2011,44,7775-7781) with the toughness reinforcing chemically crosslinked double-network hydrogel of water soluble microsphere, its tensile strength 2.46MPa, but elongation at break only reaches 1270%.Therefore a key technical problems of the two network hydrogel of synthesis is exactly make reticulated structure have certain toughness, intensity and reversibility.In hydrogel, the crosslinking method of dual network and formation mechenism directly affect the mechanical property of hydrogel, and therefore, improving the network strength of dual network and toughness is prepare the matter of utmost importance that double-network hydrogel must solve.The two net hydrogel of the hydrophobic microballoon toughen and intensify physical crosslinking that the present invention adopts overcomes the two low toughness of hydrogel and the intensity of making of net hydrogel intensity of physical crosslinking and all increases, and has no the report about hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel.
Summary of the invention
In order to solve the toughen and intensify problem of physical cross-linking hydrogel, the invention provides a kind of preparation method of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel.
Inventive point of the present invention there are provided the activeness and quietness of hydrophobic microballoon for physical crosslinking double-network hydrogel.
The preparation method of a kind of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel provided by the invention, step and condition as follows:
(1) hydrophobic microballoon emulsion is prepared
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:60-70:6-8:0.1-0.5:0.2-0.6:0.01-0.05:0.1-0.5, obtains the first pre-emulsion; Described comonomer I is butyl acrylate, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and linking agent is Vinylstyrene, and molecular weight regulator is tert-dodecyl mercaptan, and pH value buffer reagent is sodium bicarbonate;
B, the first pre-emulsion is put into four mouthfuls of reactors, and four mouthfuls of reactors are put into Water Tank with Temp.-controlled, stir and pass into nitrogen to this system, temperature remains on 50 DEG C, after the air in system is emptying, be warming up to 70 DEG C, insulation 2-4 hour, polyreaction terminates, and obtaining hydrophobic microspheres quality content is the emulsion of 35%-39.3%; Described hydrophobic microballoon is the microballoon with tridimensional network that comonomer I butyl acrylate and cross-linker divinylbenzene crosslinking copolymerization are formed;
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in the water of 40 DEG C, is made into the solution that concentration is 40mg/mL;
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon in mass ratio 100:60:4-5:0.3-0.9:1.2-1.6:0.06-0.072 the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtain the second pre-emulsion; Described comonomer II is acrylamide, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and hydrophobic monomer is hexadecyl metrhacrylate;
C, by the aqueous gelatin solution of preparation and the second pre-emulsion by volume 1:1 put into reactor, magnetic agitation 30 minutes, gets a uniform mixture;
D, the homogeneous mixture solotion obtained by above-mentioned steps c put into the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 hour, and reaction terminates, and the gel obtained is placed 6-8 hour at 10-15 DEG C, obtains hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel; Described hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel is made up of first network and second network IPN, and first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed; Second network is the micella that the hydrophobic monomer in comonomer II acrylamide and hydrophobic monomer hexadecyl metrhacrylate multipolymer forms centered by hydrophobic microballoon under emulsifying agent effect.
beneficial effect:the distinguishing feature of the hydrophobic microballoon toughness reinforcing physical crosslinking double-network hydrogel of the present invention's synthesis is to add hydrophobic microballoon.The specific surface area of hydrophobic microballoon is large, hydrophobic association ability is strong, and there is very strong heat resistance and salt tolerance between hydrophobic macromolecule, form stronger hydrophobic association center, and hydrophobic microballoon has certain strong and unyielding degree, therefore make the elongation at break of physical crosslinking double-network hydrogel reach more than 6000%, tensile strength is up to 2MPa.Solve the gordian technique of physical crosslinking double-network hydrogel toughen and intensify, widen the Application Areas of physical crosslinking double-network hydrogel.
Embodiment
embodiment 1
(1) hydrophobic microballoon emulsion is prepared
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:60:6:0.1:0.2:0.01:0.1, obtains the first pre-emulsion; Described comonomer I is butyl acrylate, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and linking agent is Vinylstyrene, and molecular weight regulator is tert-dodecyl mercaptan, and pH value buffer reagent is sodium bicarbonate;
B, the first pre-emulsion is put into four mouthfuls of reactors, and four mouthfuls of reactors are put into Water Tank with Temp.-controlled, stir and also pass into nitrogen to this system, temperature remains on 50 DEG C, after the air in system is emptying, is warming up to 70 DEG C, insulation 2-4 hour, polyreaction terminates, and obtains hydrophobic microballoon emulsion; Described hydrophobic microballoon is the microballoon with tridimensional network that comonomer I butyl acrylate and cross-linker divinylbenzene crosslinking copolymerization are formed.
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in the water of 40 DEG C, is made into the uniform and stable solution that concentration is 40mg/mL;
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon 100:60:4:0.3:1.2:0.06 in mass ratio, the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtains the second pre-emulsion; Described comonomer II is acrylamide, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and hydrophobic monomer is hexadecyl metrhacrylate;
C, by the aqueous gelatin solution of preparation and the second pre-emulsion by volume 1:1 put into reactor, magnetic agitation 30 minutes, gets a uniform mixture;
D, the homogeneous mixture solotion that above-mentioned c obtains is put into the mould of sealing, be heated to 70 DEG C, constant temperature 2-4 hour, reaction terminates, and the gel obtained is placed 6-8 hour at 10-15 DEG C, obtains hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel; Described hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel is made up of first network and second network IPN, and first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed; Second network is the micella that the hydrophobic monomer in comonomer II acrylamide and hydrophobic monomer hexadecyl metrhacrylate multipolymer forms centered by hydrophobic microballoon under emulsifying agent effect.
the measuring method of hydrophobic microspherulite diameter:hydrophobic microspherulite diameter uses the 90Plus particle instrument of Brookhaven company to measure.The emulsion droplets one of hydrophobic microballoon is dropped in sample pool, after diluting 100 times with deionized water, starts test.After repeated test 4 times, being averaged particle diameter is 212-217nm.
the measuring method of hydrophobic microballoon concentration:by the hydrophobic microballoon emulsion of preparation, weight is designated as W, and with the aluminum chloride aqueous solution breakdown of emulsion of concentration 5%, after the condensation product water obtained is rinsed 5 times repeatedly, putting into baking oven postscript of weighing after dry 8 hours is G, the calculation formula of hydrophobic microballoon concentration C:
C=（G/W）×100%
The mass concentration of hydrophobic microballoon is 35%.
the mechanics performance determining method of the hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel of preparation:in swelling equilibrium state, hydrogel being cut into width is 4cm, thickness is 1cm, length is the dumbbell shaped of 6cm, 3 samples prepared by the hydrogel prepared under each embodiment condition, and Instron6022 universal testing machine carries out mechanical stretch experiment, and gauge length is 15mm, rate of extension is 20mm/min, measures its mechanical property;
Tensile strength is calculated as follows:
In formula: P is ultimate load, unit is N; B is specimen width, and unit is mm; D is sample thickness, and unit is mm.
Tensile deformation is calculated as follows:
In formula:
lbe the length that drawing machine stretches, unit is cm;
l 0 be batten original length, unit is cm.
The tensile strength of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel prepared by embodiment 1 and elongation at break averages are respectively 2.07MPa and 6090%.
embodiment 2
(1) hydrophobic microballoon emulsion is prepared
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:65:7:0.3:0.4:0.03:0.3, obtains the first pre-emulsion; Described comonomer I is butyl acrylate, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and linking agent is Vinylstyrene, and molecular weight regulator is tert-dodecyl mercaptan, and pH value buffer reagent is sodium bicarbonate;
B, the first pre-emulsion is put into four mouthfuls of reactors, and four mouthfuls of reactors are put into Water Tank with Temp.-controlled, stir and also pass into nitrogen to this system, temperature remains on 50 DEG C, after the air in system is emptying, is warming up to 70 DEG C, insulation 2-4 hour, polyreaction terminates, and obtains hydrophobic microballoon emulsion; Described hydrophobic microballoon is the microballoon with tridimensional network that comonomer I butyl acrylate and cross-linker divinylbenzene crosslinking copolymerization are formed.
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in the water of 40 DEG C, is made into the uniform and stable solution that concentration is 40mg/mL;
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon 100:60:4.5:0.6:1.4:0.07 in mass ratio, the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtains the second pre-emulsion; Described comonomer II is acrylamide, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and hydrophobic monomer is hexadecyl metrhacrylate;
C, by the aqueous gelatin solution of preparation and the second pre-emulsion by volume 1:1 put into reactor, magnetic agitation 30 minutes, gets a uniform mixture;
D, the homogeneous mixture solotion that above-mentioned c obtains is put into the mould of sealing, be heated to 70 DEG C, constant temperature 2-4 hour, reaction terminates, and the gel obtained is placed 6-8 hour at 10-15 DEG C, obtains hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel; Described hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel is made up of first network and second network IPN, and first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed; Second network is the micella that the hydrophobic monomer in comonomer II acrylamide and hydrophobic monomer hexadecyl metrhacrylate multipolymer forms centered by hydrophobic microballoon under emulsifying agent effect.
With the measuring method of example 1, the median size that hydrophobic microballoon prepared by embodiment 2 measures is 300-306nm.
With the measuring method of example 1, hydrophobic microballoon quality of the emulsion concentration prepared by embodiment 2 is 37.5%.
With the measuring method of example 1, the tensile strength of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel prepared by embodiment 2 and elongation at break averages are respectively 2.12MPa and 6150%.
embodiment 3
(1) hydrophobic microballoon emulsion is prepared
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:70:8:0.5:0.6:0.05:0.5, obtains the first pre-emulsion; Described comonomer I is butyl acrylate, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and linking agent is Vinylstyrene, and molecular weight regulator is tert-dodecyl mercaptan, and pH value buffer reagent is sodium bicarbonate;
B, the first pre-emulsion is put into four mouthfuls of reactors, and four mouthfuls of reactors are put into Water Tank with Temp.-controlled, stir and also pass into nitrogen to this system, temperature remains on 50 DEG C, after the air in system is emptying, is warming up to 70 DEG C, insulation 2-4 hour, polyreaction terminates, and obtains hydrophobic microballoon emulsion; Described hydrophobic microballoon is the microballoon with tridimensional network that comonomer I butyl acrylate and cross-linker divinylbenzene crosslinking copolymerization are formed.
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in the water of 40 DEG C, is made into the uniform and stable solution that concentration is 40mg/mL;
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon 100:60:5:0.9:1.6:0.072 in mass ratio, the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtains the second pre-emulsion; Described comonomer II is acrylamide, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and hydrophobic monomer is hexadecyl metrhacrylate;
C, by the aqueous gelatin solution of preparation and the second pre-emulsion by volume 1:1 put into reactor, magnetic agitation 30 minutes, gets a uniform mixture;
D, the homogeneous mixture solotion that above-mentioned c obtains is put into the mould of sealing, be heated to 70 DEG C, constant temperature 2-4 hour, reaction terminates, and the gel obtained is placed 6-8 hour at 10-15 DEG C, obtains hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel; Described hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel is made up of first network and second network IPN, and first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed; Second network is the micella that the hydrophobic monomer in comonomer II acrylamide and hydrophobic monomer hexadecyl metrhacrylate multipolymer forms centered by hydrophobic microballoon under emulsifying agent effect.
With the measuring method of example 1, the median size that hydrophobic microballoon prepared by embodiment 3 measures is 419-425nm.
With the measuring method of example 1, hydrophobic microballoon quality of the emulsion concentration prepared by embodiment 3 is 39.3%.
With the measuring method of example 1, the tensile strength of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel prepared by embodiment 3 and elongation at break averages are respectively 2.19MPa and 6120%.
Claims (4)
1. a preparation method for hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel, is characterized in that, step and condition as follows:
(1) hydrophobic microballoon emulsion is prepared
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:60-70:6-8:0.1-0.5:0.2-0.6:0.01-0.05:0.1-0.5, obtains the first pre-emulsion; Described comonomer I is butyl acrylate, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and linking agent is Vinylstyrene, and molecular weight regulator is tert-dodecyl mercaptan, and pH value buffer reagent is sodium bicarbonate;
B, the first pre-emulsion is put into four mouthfuls of reactors, and four mouthfuls of reactors are put into Water Tank with Temp.-controlled, stir and also pass into nitrogen to this system, temperature remains on 50 DEG C, after the air in system is emptying, is warming up to 70 DEG C, insulation 2-4 hour, polyreaction terminates, and obtains the emulsion of hydrophobic microballoon; Described hydrophobic microballoon is the microballoon with tridimensional network that comonomer I butyl acrylate and cross-linker divinylbenzene crosslinking copolymerization are formed;
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in the water of 40 DEG C, is made into the solution that concentration is 40mg/mL;
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon 100:60:4-5:0.3-0.9:1.2-1.6:0.06-0.072 in mass ratio, the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtains the second pre-emulsion; Described comonomer II is acrylamide, and emulsifying agent is sodium laurylsulfonate, and initiator is Potassium Persulphate, and hydrophobic monomer is hexadecyl metrhacrylate;
C, by the aqueous gelatin solution of preparation and the second pre-emulsion by volume 1:1 put into reactor, magnetic agitation 30 minutes, gets a uniform mixture;
D, the homogeneous mixture solotion obtained by above-mentioned steps c put into the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 hour, and reaction terminates, and the gel obtained is placed 6-8 hour at 10-15 DEG C, obtains hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel; Described hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel is made up of first network and second network IPN, and first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed; Second network is the micella that the hydrophobic monomer in comonomer II acrylamide and hydrophobic monomer hexadecyl metrhacrylate multipolymer forms centered by hydrophobic microballoon under emulsifying agent effect.
2. the preparation method of a kind of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel as claimed in claim 1, it is characterized in that, described (1) prepares hydrophobic microballoon emulsion
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:60:6:0.1:0.2:0.01:0.1, obtains the first pre-emulsion
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon 100:60:4:0.3:1.2:0.06 in mass ratio, the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtains the second pre-emulsion.
3. the preparation method of a kind of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel as claimed in claim 1, it is characterized in that, described (1) prepares hydrophobic microballoon emulsion
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:65:7:0.3:0.4:0.03:0.3, obtains the first pre-emulsion;
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon in mass ratio 100:60:4.5:0.6:1.4:0.07 the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtain the second pre-emulsion.
4. the preparation method of a kind of hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel as claimed in claim 1, it is characterized in that, described (1) prepares hydrophobic microballoon emulsion
A, prepare the first pre-emulsion
Water, comonomer I, emulsifying agent, initiator, linking agent, molecular weight regulator and pH value buffer reagent are mixed according to mass ratio 100:70:8:0.5:0.6:0.05:0.5, obtains the first pre-emulsion;
(2) one kettle way prepares hydrophobic microballoon toughen and intensify physical crosslinking double-network hydrogel
B, prepare the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon in mass ratio 100:60:5:0.9:1.6:0.072 the emulsion of water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microballoon is mixed, obtain the second pre-emulsion.
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