CN105085791B - 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 the synthesis of hydrogel and activeness and quietness technology, it is related to a kind of toughness reinforcing enhancing of hydrophobic microsphere and is physical crosslinking
The preparation method of double-network hydrogel.
Background technology
Hydrogel is the macromolecular material with three-dimensional netted cross-linked structure.Hydrophilic big due to being mainly in molecular structure
Molecule, so substantial amounts of water can be absorbed.Hydrogel properties are soft, similar to vital tissues material, have good biocompatibility,
Therefore it is widely used in organizational project, medicinal slow release agent, tissue stent material etc..But most of hydrogels are because its mechanical property
Can the poor application needing high-toughness high-strength hydrogel at some be restricted, such as tendon, cartilage etc..Chinese state
Interior a lot of scholar is devoted to studying raising and the improvement of hydrogel mechanical property.Successively achieve macromole topology hydrogel,
Nanometer composite hydrogel, double-network hydrogel, macromolecular microspheres cross-linked hydrogel, hydrophobic association hydrogel etc..And China's water-setting
The research and development of glue is later, and the technical merit of hydrogel material and application level are had necessarily with the developed country such as Japan, U.S.
Gap, China required for hydrogel major part be import, therefore, the R and D of hydrogel have ten to Chinese market
Divide important meaning.
Although traditional double-network hydrogel improves the mechanical property of hydrogel to a great extent, for example traditional change
Learning first network in crosslinked double-network hydrogel is strong electrolyte, ruptures broken, fine grained chippings becomes the second network in drawing process
Stress branch and physical crosslinking point, enable the power performance deficiency of the second network to reduce, the mechanical property of hydrogel increases, but
It is not met by the requirement to hydrogel mechanical property.In order to further improve the mechanical property of double-network hydrogel, research
Worker is achieved with certain effect.Domestic Institutes Of Technology Of He'nan Chen Qiang etc.（A Novel Design Strategy for
Fully Physically Linked Double Network Hydrogels with Tough,Fatigue
Resistant,and Self-Healing Properties ,2015）It is prepared for being physical crosslinking double-network hydrogel.Physics is handed over
Connection 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.Hokkaido, Japan university Gong Jian duckweed etc.（ Microgel-Reinforced
Hydrogel Films with High Mechanical Strength and Their Visible Mesoscale
Fracture Structure,Macromolecules,2011,44,7775-7781）With the toughness reinforcing chemical crosslinking of water soluble microsphere
Double-network hydrogel, its tensile strength 2.46MPa, but elongation at break only reaches 1270%,.Therefore synthesize double network hydrogels
One key technical problems is exactly to make network structure have certain toughness, intensity and reversibility.The friendship of dual network in hydrogel
Connection mode and formation mechenism directly affect the mechanical property of hydrogel, and therefore, improving the network strength of dual network and toughness is system
The matter of utmost importance that standby double-network hydrogel must solve.The toughness reinforcing enhancing of hydrophobic microsphere that the present invention adopts is physical crosslinking double net water-settings
Glue overcome physical crosslinking double net hydrogel intensity is low so that the toughness of hydrogel and intensity is all increased, and have no relevant hydrophobic
The toughness reinforcing report strengthening physical crosslinking double-network hydrogel of microsphere.
Content of the invention
In order to solve the problems, such as the toughness reinforcing enhancing of physical cross-linking hydrogel, the invention provides a kind of toughness reinforcing enhancing of hydrophobic microsphere
The preparation method of physical crosslinking double-network hydrogel.
The inventive point of the present invention there are provided hydrophobic microsphere for being physical crosslinking the activeness and quietness of double-network hydrogel.
The present invention provide a kind of hydrophobic microsphere toughness reinforcing strengthen physical crosslinking double-network hydrogel preparation method, step and
Condition is as follows：
(1) prepare hydrophobic microsphere emulsion
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to quality
Ratio 100：60-70：6-8：0.1-0.5：0.2-0.6：0.01-0.05：0.1-0.5 mix homogeneously, obtains the first pre-emulsion；Described
Comonomer I be butyl acrylate, emulsifying agent be dodecyl sodium sulfate, initiator be potassium peroxydisulfate, cross-linking agent be diethyl
Alkenyl benzene, molecular weight regulator is tert-dodecyl mercaptan, and pH value buffer agent is sodium bicarbonate；
B, the first pre-emulsion is put in four mouthfuls of reactors, and four mouthfuls of reactors are put in thermostatic water bath, stirring is simultaneously
It is passed through nitrogen to this system, temperature is maintained at 50 DEG C, after the air emptying in system, be warming up to 70 DEG C, be incubated 2-4 hour,
Polyreaction terminates, and obtains the emulsion that hydrophobic microspheres quality content is 35%-39.3%；Described hydrophobic microsphere is comonomer I
The microsphere with tridimensional network that butyl acrylate is formed with cross-linker divinylbenzene crosslinking copolymerization；
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in 40 DEG C of water, is made into the solution that concentration is 40mg/mL；
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：4-5：
0.3-0.9:1.2-1.6:0.06-0.072 is by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere
Emulsion mix homogeneously, obtains the second pre-emulsion；Described comonomer II is acrylamide, and emulsifying agent is dodecyl sodium sulfonate
Sodium, initiator is potassium peroxydisulfate, and hydrophobic monomer is hexadecyl metrhacrylate；
C, by the aqueous gelatin solution prepared and the second pre-emulsion by volume 1：1 puts in reactor, magnetic agitation 30
Minute, get a uniform mixture；
D, the homogeneous mixture solotion obtaining above-mentioned steps c are put in the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 is little
When, reaction terminates, and the gel obtaining is placed 6-8 hour at 10-15 DEG C, obtains toughness reinforcing enhancing of hydrophobic microsphere and is physical crosslinking double nets
Network hydrogel；The toughness reinforcing physical crosslinking double-network hydrogel that strengthens of described hydrophobic microsphere is by first network and the second network interpenetrating
Constitute, first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed；Second network is comonomer
Hydrophobic monomer in II acrylamide and hydrophobic monomer hexadecyl metrhacrylate copolymer is formed to dredge under emulsifying agent effect
Micelle centered on water microsphere.
Beneficial effect：The distinguishing feature of the hydrophobic microsphere toughness reinforcing physical crosslinking double-network hydrogel of present invention synthesis is to add
Enter hydrophobic microsphere.The specific surface area of hydrophobic microsphere is big, and hydrophobic association ability is strong, has very strong hydrophobic association and between hydrophobic macromolecule
Effect, forms stronger hydrophobic association center, and hydrophobic microsphere has certain strong and unyielding degree, therefore makes physical crosslinking dual network water
The elongation at break of gel reaches more than 6000%, and tensile strength is up to 2MPa.Solve physical crosslinking double-network hydrogel toughness reinforcing
Enhanced key technology, has widened the application of physical crosslinking double-network hydrogel.
Specific embodiment
Embodiment 1
(1) prepare hydrophobic microsphere emulsion
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to quality
Ratio 100：60：6：0.1：0.2：0.01：0.1 mix homogeneously, obtains the first pre-emulsion；Described comonomer I is acrylic acid fourth
Ester, emulsifying agent is dodecyl sodium sulfate, and initiator is potassium peroxydisulfate, and cross-linking agent is divinylbenzene, and molecular weight regulator is
Tert-dodecyl mercaptan, pH value buffer agent is sodium bicarbonate；
B, the first pre-emulsion is put in four mouthfuls of reactors, and four mouthfuls of reactors are put in thermostatic water bath, stirring is simultaneously
It is passed through nitrogen to this system, temperature is maintained at 50 DEG C, after the air emptying in system, be warming up to 70 DEG C, be incubated 2-4 hour,
Polyreaction terminates, and obtains hydrophobic microsphere emulsion；Described hydrophobic microsphere is comonomer I butyl acrylate and cross-linking agent two
The microsphere with tridimensional network that vinyl benzene crosslinking copolymerization is formed.
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in 40 DEG C of water, is made into the uniform and stable solution that concentration is 40mg/mL；
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：4：0.3：
1.2：0.06, by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion mix homogeneously, obtain
Second pre-emulsion；Described comonomer II is acrylamide, and emulsifying agent is dodecyl sodium sulfate, and initiator is persulfuric acid
Potassium, hydrophobic monomer is hexadecyl metrhacrylate；
C, by the aqueous gelatin solution prepared and the second pre-emulsion by volume 1：1 puts in reactor, magnetic agitation 30
Minute, get a uniform mixture；
D, the homogeneous mixture solotion obtaining above-mentioned c are put in the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 hour, instead
Should terminate, the gel obtaining is placed 6-8 hour at 10-15 DEG C, obtain toughness reinforcing enhancing of hydrophobic microsphere and be physical crosslinking dual network water
Gel；The toughness reinforcing physical crosslinking double-network hydrogel that strengthens of described hydrophobic microsphere is to be made up of first network and the second network interpenetrating
, first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed；Second network is comonomer II third
Hydrophobic monomer in acrylamide and hydrophobic monomer hexadecyl metrhacrylate copolymer is formed with hydrophobic micro- under emulsifying agent effect
Micelle centered on ball.
The assay method of hydrophobic microspherulite diameter：Hydrophobic microspherulite diameter uses the 90Plus particle instrument of Brookhaven company to survey
Fixed.The emulsion droplets one of hydrophobic microsphere are dropped in sample cell, after deionized water dilutes 100 times, starts to test.Retest 4
After secondary, average particle diameter is taken to be 212-217nm.
The assay method of hydrophobic microsphere concentration：By the hydrophobic microsphere emulsion of preparation, weight is designated as W, with the trichlorine of concentration 5%
Change aluminum water solution breakdown of emulsion, the condensation product obtaining water is rinsed after 5 times repeatedly, put into postscript of weighing after being dried 8 hours in baking oven
For G, the computing formula of hydrophobic microsphere concentration C：
C=（G/W）×100%
The mass concentration of hydrophobic microsphere is 35%.
The toughness reinforcing mechanics performance determining method strengthening physical crosslinking double-network hydrogel of hydrophobic microsphere of preparation：Swelling flat
Weighing apparatus state, it is 4cm that hydrogel is cut into width, and thickness is 1cm, and length is the dumbbell shaped of 6cm, prepares under the conditions of each embodiment
Hydrogel prepare 3 samples, mechanical stretch experiment is carried out on Instron6022 universal testing machine, gauge length be 15mm,
Rate of extension is 20mm/min, measures its mechanical property；
Tensile strength is calculated as follows:
In formula：P is maximum load, and 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：LIt is the length of stretching-machine stretching, unit is cm；L 0 It is batten original length, unit is cm.
The toughness reinforcing tensile strength strengthening physical crosslinking double-network hydrogel of the hydrophobic microsphere of embodiment 1 preparation and extension at break
Rate meansigma methodss are respectively 2.07 MPa and 6090%.
Embodiment 2
(1) prepare hydrophobic microsphere emulsion
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to quality
Ratio 100：65：7：0.3：0.4：0.03：0.3 mix homogeneously, obtains the first pre-emulsion；Described comonomer I is acrylic acid fourth
Ester, emulsifying agent is dodecyl sodium sulfate, and initiator is potassium peroxydisulfate, and cross-linking agent is divinylbenzene, and molecular weight regulator is
Tert-dodecyl mercaptan, pH value buffer agent is sodium bicarbonate；
B, the first pre-emulsion is put in four mouthfuls of reactors, and four mouthfuls of reactors are put in thermostatic water bath, stirring is simultaneously
It is passed through nitrogen to this system, temperature is maintained at 50 DEG C, after the air emptying in system, be warming up to 70 DEG C, be incubated 2-4 hour,
Polyreaction terminates, and obtains hydrophobic microsphere emulsion；Described hydrophobic microsphere is comonomer I butyl acrylate and cross-linking agent two
The microsphere with tridimensional network that vinyl benzene crosslinking copolymerization is formed.
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in 40 DEG C of water, is made into the uniform and stable solution that concentration is 40mg/mL；
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：4.5：
0.6：1.4：0.07, by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion mix homogeneously,
Obtain the second pre-emulsion；Described comonomer II is acrylamide, and emulsifying agent is dodecyl sodium sulfate, and initiator was
Potassium sulfate, hydrophobic monomer is hexadecyl metrhacrylate；
C, by the aqueous gelatin solution prepared and the second pre-emulsion by volume 1：1 puts in reactor, magnetic agitation 30
Minute, get a uniform mixture；
D, the homogeneous mixture solotion obtaining above-mentioned c are put in the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 hour, instead
Should terminate, the gel obtaining is placed 6-8 hour at 10-15 DEG C, obtain toughness reinforcing enhancing of hydrophobic microsphere and be physical crosslinking dual network water
Gel；The toughness reinforcing physical crosslinking double-network hydrogel that strengthens of described hydrophobic microsphere is to be made up of first network and the second network interpenetrating
, first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed；Second network is comonomer II third
Hydrophobic monomer in acrylamide and hydrophobic monomer hexadecyl metrhacrylate copolymer is formed with hydrophobic micro- under emulsifying agent effect
Micelle centered on ball.
With the assay method of example 1, the mean diameter that the hydrophobic microsphere of embodiment 2 preparation measures is 300-306nm.
With the assay method of example 1, the hydrophobic microsphere quality of the emulsion concentration of embodiment 2 preparation is 37.5%.
With the assay method of example 1, the hydrophobic microsphere of embodiment 2 preparation is toughness reinforcing to strengthen physical crosslinking double-network hydrogel
Tensile strength and elongation at break averages are respectively 2.12 MPa and 6150%.
Embodiment 3
(1) prepare hydrophobic microsphere emulsion
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to quality
Ratio 100：70：8：0.5：0.6：0.05：0.5 mix homogeneously, obtains the first pre-emulsion；Described comonomer I is acrylic acid fourth
Ester, emulsifying agent is dodecyl sodium sulfate, and initiator is potassium peroxydisulfate, and cross-linking agent is divinylbenzene, and molecular weight regulator is
Tert-dodecyl mercaptan, pH value buffer agent is sodium bicarbonate；
B, the first pre-emulsion is put in four mouthfuls of reactors, and four mouthfuls of reactors are put in thermostatic water bath, stirring is simultaneously
It is passed through nitrogen to this system, temperature is maintained at 50 DEG C, after the air emptying in system, be warming up to 70 DEG C, be incubated 2-4 hour,
Polyreaction terminates, and obtains hydrophobic microsphere emulsion；Described hydrophobic microsphere is comonomer I butyl acrylate and cross-linking agent two
The microsphere with tridimensional network that vinyl benzene crosslinking copolymerization is formed.
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in 40 DEG C of water, is made into the uniform and stable solution that concentration is 40mg/mL；
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：5：0.9：
1.6：0.072, by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion mix homogeneously, obtain
Second pre-emulsion；Described comonomer II is acrylamide, and emulsifying agent is dodecyl sodium sulfate, and initiator is persulfuric acid
Potassium, hydrophobic monomer is hexadecyl metrhacrylate；
C, by the aqueous gelatin solution prepared and the second pre-emulsion by volume 1：1 puts in reactor, magnetic agitation 30
Minute, get a uniform mixture；
D, the homogeneous mixture solotion obtaining above-mentioned c are put in the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 hour, instead
Should terminate, the gel obtaining is placed 6-8 hour at 10-15 DEG C, obtain toughness reinforcing enhancing of hydrophobic microsphere and be physical crosslinking dual network water
Gel；The toughness reinforcing physical crosslinking double-network hydrogel that strengthens of described hydrophobic microsphere is to be made up of first network and the second network interpenetrating
, first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed；Second network is comonomer II third
Hydrophobic monomer in acrylamide and hydrophobic monomer hexadecyl metrhacrylate copolymer is formed with hydrophobic micro- under emulsifying agent effect
Micelle centered on ball.
With the assay method of example 1, the mean diameter that the hydrophobic microsphere of embodiment 3 preparation measures is 419-425nm.
With the assay method of example 1, the hydrophobic microsphere quality of the emulsion concentration of embodiment 3 preparation is 39.3%.
With the assay method of example 1, the hydrophobic microsphere of embodiment 3 preparation is toughness reinforcing to strengthen physical crosslinking double-network hydrogel
Tensile strength and elongation at break averages are respectively 2.19 MPa and 6120%.
Claims (4)
1. a kind of toughness reinforcing preparation method strengthening physical crosslinking double-network hydrogel of hydrophobic microsphere is it is characterised in that step and bar
Part is as follows：
(1) prepare hydrophobic microsphere emulsion
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH 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 mix homogeneously, obtains the first pre-emulsion；Described
Comonomer I is butyl acrylate, and emulsifying agent is dodecyl sodium sulfate, and initiator is potassium peroxydisulfate, and cross-linking agent is divinyl
Base benzene, molecular weight regulator is tert-dodecyl mercaptan, and pH is sodium bicarbonate；
B, the first pre-emulsion is put in four mouthfuls of reactors, and four mouthfuls of reactors are put in thermostatic water bath, stirring to this
System is passed through nitrogen, and temperature is maintained at 50 DEG C, after the air emptying in system, is warming up to 70 DEG C, is incubated 2-4 hour, polymerization
Reaction terminates, and obtains the emulsion of hydrophobic microsphere；Described hydrophobic microsphere is comonomer I butyl acrylate and cross-linking agent divinyl
The microsphere with tridimensional network that base benzene crosslinking copolymerization is formed；
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
A, preparation aqueous gelatin solution
Gelatin is dissolved in 40 DEG C of water, is made into the solution that concentration is 40mg/mL；
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：4-5：0.3-
0.9:1.2-1.6:0.06-0.072, by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion
Mix homogeneously, obtains the second pre-emulsion；Described comonomer II is acrylamide, and emulsifying agent is dodecyl sodium sulfate,
Initiator is potassium peroxydisulfate, and hydrophobic monomer is hexadecyl metrhacrylate；
C, by the aqueous gelatin solution prepared and the second pre-emulsion by volume 1：1 puts in reactor, magnetic agitation 30 minutes,
Get a uniform mixture；
D, the homogeneous mixture solotion obtaining above-mentioned steps c are put in the mould of sealing, are heated to 70 DEG C, constant temperature 2-4 hour, instead
Should terminate, the gel obtaining is placed 6-8 hour at 10-15 DEG C, obtain toughness reinforcing enhancing of hydrophobic microsphere and be physical crosslinking dual network water
Gel；The toughness reinforcing physical crosslinking double-network hydrogel that strengthens of described hydrophobic microsphere is to be made up of first network and the second network interpenetrating
, first network is the double-spiral structure that the mutual hydrogen bond action of Gelatin Macromolecule chain is formed；Second network is comonomer II third
Hydrophobic monomer in acrylamide and hydrophobic monomer hexadecyl metrhacrylate copolymer is formed with hydrophobic micro- under emulsifying agent effect
Micelle centered on ball.
2. a kind of hydrophobic microsphere is toughness reinforcing as claimed in claim 1 strengthens the preparation method being physical crosslinking double-network hydrogel, its
It is characterised by, hydrophobic microsphere emulsion is prepared in described (1)
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to mass ratio
100：60：6：0.1：0.2：0.01：0.1 mix homogeneously, obtains the first pre-emulsion
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：4：0.3：1.2：
0.06, by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion mix homogeneously, obtain second
Pre-emulsion.
3. a kind of hydrophobic microsphere is toughness reinforcing as claimed in claim 1 strengthens the preparation method being physical crosslinking double-network hydrogel, its
It is characterised by, hydrophobic microsphere emulsion is prepared in described (1)
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to mass ratio
100：65：7：0.3：0.4：0.03：0.3 mix homogeneously, obtains the first pre-emulsion；
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：4.5：0.6：
1.4：0.07 by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion mix homogeneously, obtain
Two pre-emulsions.
4. a kind of hydrophobic microsphere is toughness reinforcing as claimed in claim 1 strengthens the preparation method being physical crosslinking double-network hydrogel, its
It is characterised by, hydrophobic microsphere emulsion is prepared in described (1)
A, preparation the first pre-emulsion
By water, comonomer I, emulsifying agent, initiator, cross-linking agent, molecular weight regulator and pH according to mass ratio
100：70：8：0.5：0.6：0.05：0.5 mix homogeneously, obtains the first pre-emulsion；
(2) one kettle way prepares hydrophobic microsphere toughness reinforcing enhancing physical crosslinking double-network hydrogel
B, preparation the second pre-emulsion
By water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere in mass ratio 100：60：5：0.9：1.6：
0.072 by water, comonomer II, emulsifying agent, initiator, hydrophobic monomer and hydrophobic microsphere emulsion mix homogeneously, obtain second
Pre-emulsion.
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| CN102942699B (en) * | 2012-10-26 | 2014-07-02 | 暨南大学 | Self-reinforced bi-crosslinking hyaluronic acid hydrogel and preparation method thereof |
| CN103739861A (en) * | 2014-01-02 | 2014-04-23 | 河南理工大学 | Preparation method of high-strength hydrogel |
| CN103848937B (en) * | 2014-01-09 | 2016-01-20 | 湖北工业大学 | A kind of can the preparation method of the tired high strength double-layer network hydrogel repaired |
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