CN103739861A - Preparation method of high-strength hydrogel - Google Patents
Preparation method of high-strength hydrogel Download PDFInfo
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- CN103739861A CN103739861A CN201410000801.8A CN201410000801A CN103739861A CN 103739861 A CN103739861 A CN 103739861A CN 201410000801 A CN201410000801 A CN 201410000801A CN 103739861 A CN103739861 A CN 103739861A
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Abstract
The invention relates to a high-strength hydrogel and a preparation method thereof. The preparation method comprises the steps of directly mixing a polymer, a monomer, an initiator, a cross-linking agent and water once, dissolving all the substances to form a homogeneous solution under a certain simulation condition, and then initiating and polymerizing by using heat or light to obtain the high-strength hydrogel, wherein the polymer is needed for preparation of the hydrogel and used for forming a first double network of a dual-network hydrogel; the monomer is used for polymerizing and forming a second double network of the dual-network hydrogel; the initiator is used for initiating the monomer to be polymerized; the cross-linking agent is used for performing cross-linking reaction in a monomer polymerizing process so as to form the second double network. According to the preparation method, a one-pot method is used for preparing the high-strength hydrogel, so that the method is simple and practicable; the prepared high-strength hydrogel has the characteristics of high strength and high toughness; a tensile strength of the gel is 0.6-1.2MPa, a tensile modulus is 100-200 KPa and a tensile strain reaches 1000-2680%; the prepared high-strength hydrogel can be widely applied to the fields of tissue repair, artificial organ, drug sustained release, sensors and the like.
Description
Technical field
The present invention relates to a kind of hydrogel, specifically a kind of preparation method of high intensity hydrogel.
Background technology
Hydrogel is the macromolecular material with three-dimensional net structure that chemically crosslinked or physical crosslinking form, and contains a large amount of water and soft-touch, can keep definite shape in macromolecule network, and this characteristic and organism soft tissue have a lot of similaritys.Hydrogel has the character of solid and liquid two aspects conventionally concurrently, there is the outside atmosphere of replying and change the characteristic of self shape or state, thereby adsorbable, desorption is attached, carry, see through material, have hold, the function of separation, sustained-release materials.These unique textures and the function of hydrogel, make to have wide development and application prospect at aspects such as life science, Food science, selective adsorption, medicine controlled releasing, biosensor and organizational projects.
But, the hydrogel soft that general chemistry is crosslinked and a little less than, intensity is low, the little scope that limits its application of deformation.The high intensity hydrogel exploitation with tough character has become recent study hotspot both domestic and external.Some investigators have carried out a large amount of research work for the mechanical property that improves hydrogel, occurred that several classes have the high-strength gel of novel structure and good mechanical property, these gels comprise double-network hydrogel, material > > (Soft Matter as soft in < <, 2010, 6, 2583-2590), deliver survey article " why double-network hydrogel is so tough? " (J.P.Gong, Why are double network hydrogels so tough?), nano-composite gel, as < < applied chemistry > > (Angew. Chem. Int. Ed.2005,44,6500-6504) on deliver article " superelevation mechanical property poly-(
n-N-isopropylacrylamide) Nanometer composite hydrogel " (K.Haraguchi, H.J.Li Control of the Coil-to-Globule Transition and Ultrahigh Mechanical Properties of PNIPA in Nanocomposite Hydrogels), hydrophobic association gel, material > > (Soft Matter as soft in < <, 2012, 8, the article delivered 5078-5086) " shows the high mechanical strength hydrophobic association gel of reactive monomer " based on acrylamide and negatively charged ion (W.B. Li, H.Y. An, Y. Tan, C.G. Lu, C. Liu, P.C. Li, K. Xu, P.X. Wang, Hydrophobically Associated Hydrogels Based on Acrylamide and Anionic Surface Active Monomer with High Mechanical Strength), macromolecular microspheres is the plural gel of linking agent, as < < advanced material > > (Adv.Mater.2007, 19, article " a kind of novel hydrogel with high mechanical strength: macromolecular microspheres matrix material the hydrogel " (T.Huang delivering 1622-1626), H.Xu, K.Jiao, L.Zhu, H.R.Brown, H.Wang, A Novel Hydrogel with High Mechanical Strength:A Macromolecular Microsphere Composite Hydrogel), tetra-PEG hydrogel, as < < macromole (Macromolecules2008,41, article " a kind of design of high intensity hydrogel of desirable uniform texture and the preparation " (T.Sakai delivering 5379-5384), U.-i.Chung, et al.Design and Fabrication of a High-Strength Hydrogel with Ideally Homogeneous Network Structure from Tetrahedron-like Macromonomers) etc.
Although the design of high intensity hydrogel and preparation have obtained some important achievements, but the general complicated and time consumption of the preparation technology who reports at present high intensity hydrogel or the loaded down with trivial details step complex functionality monomer of needs, this has all limited the application in every field of high intensity hydrogel.Therefore, with a kind of simply, fast, method is prepared tough high intensity hydrogel and is remained a huge challenge and urgent task flexibly.
Summary of the invention
The present invention seeks to the deficiency for solving the problems of the technologies described above, the method for a kind of " treating different things alike " legal system for high intensity hydrogel is provided, preparation technology is simple, only needs 1-2h; Prepared double-network hydrogel or interpenetration network hydrogel, have excellent mechanical property and toughness.
The present invention for solving the problems of the technologies described above adopted technical scheme is:
A kind of high intensity hydrogel is double-network hydrogel or interpenetration network hydrogel; Its tensile strength is that 1.0 MPa, tensile modulus are that 100-200 KPa, tension strain reach 1000-2500%, and compressive strength is that 30-40 MPa, modulus of compression are that 100-200 KPa, compressive strain are greater than 95%, and toughness reaches 10
2-10
4j/m
2.
A kind of preparation method of high intensity hydrogel, its concrete preparation method is, described high intensity hydrogel adopts the method for " treating different things alike ", be about to hydrogel and prepare the required polymkeric substance that weighs network in order to form first of dual network gel, in order to polymerization, form the monomer of the second heavy network of double-network hydrogel, in order to the initiator of trigger monomer polymerization, thereby with forming the direct disposable mixing such as the linking agent of the second heavy network and water so that there is crosslinking reaction in monomer polymerization process simultaneously, by certain incentive condition, all substances are dissolved and form homogeneous phase solution, then reusable heat or light initiation polymerization just obtain high intensity hydrogel,
Described is one or more the combination in agar, agarose, gelatin, collagen protein, scleroproein, alginates, hyaluronate, chondroitin sulfate, carrageenin, gellan gum, guar gum, sesbania gum, chitosan, Sumstar 190 in order to form the polymkeric substance of the first heavy network of dual network gel;
The monomer of described the second heavy network in order to polymerization formation double-network hydrogel is acrylamide, N, the combination of one or more in N'-DMAA, vinylformic acid and salt thereof, methacrylic acid and salt thereof, stearyl methacrylate, methacrylic acid laurate, polyethyleneglycol diacrylate;
The described initiator in order to trigger monomer polymerization is 2,2-diethoxy acetophenone, 2-hydroxyl-4'-(2-hydroxy ethoxy) one in-2-methyl phenyl ketone, 1-hydroxy-cyclohexyl Propiophenone, 2-oxopentanedioic acid, Ammonium Persulfate 98.5, Potassium Persulphate;
Thereby described use is so that the linking agent that crosslinking reaction forms the second heavy network occurs in monomer polymerization process is N simultaneously, the one in N'-methylene-bisacrylamide, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), polyethyleneglycol diacrylate;
Described certain incentive condition is heating, illumination, pH.
A preparation method for high intensity hydrogel, the preferred following scheme of its preparation method; Concrete preparation process is:
Step 2, the mixed reaction solution in reactor is stirred at 60-90 ℃ to 5-10 min and make it form homogeneous phase transparent settled solution; Transparent gained settled solution irradiation 1-2 h under the ultraviolet lamp of 365 nm is made to high intensity hydrogel.
In the time of can being chosen in mixing water gel in its preparation method and preparing required each material, add supplementary additive, described supplementary additive is one or more the combination in tensio-active agent, divalent metal, trivalent metal cation, small molecule salt; Described tensio-active agent is sodium laurylsulfonate, sodium lauryl sulphate or cetyl trimethylammonium bromide; Described divalent metal is Ca
2+, Cu
2+, Zn
2+, Co
2+, Sr
2+or Ba
2+; Described trivalent metal cation is Fe
3+, Al
3+or Eu
3+; Described small molecule salt is NaCl or NaSCN; The total amount of adding is 0-5 mol/L.
Beneficial effect is:
1, it is simple that the present invention prepares high intensity hydrogel employing " treating different things alike " method, avoided conventionally preparing the swelling process that double-network hydrogel or interpenetration network hydrogel must pass through, preparation technology consuming time short, energy consumption is little, the preparation of gel only needs 1-2 h just can complete.The method has been utilized the controlled sol-gel transition of polymkeric substance, and the high intensity hydrogel of preparation can return to initial structure and high strength after by outside destroy structure under extraneous incentive condition or non-stimulated condition; Raw material is simple and easy to get, without the modification through complicated; Preparation process green safety, and prepared high intensity hydrogel harmless, also can not cause secondary pollution to environment, for preparation functionalization high intensity hydrogel provides approach.
2, the prepared high intensity hydrogel of the present invention, double-network hydrogel or interpenetration network hydrogel, in the raw material that can prepare by control, add, thus in order to form dual network gel the first heavy network polymkeric substance, in order to polymerization form the second heavy network of double-network hydrogel monomer, initiator in order to trigger monomer polymerization, use so that the amount of linking agent, supplementary additive and the water of crosslinking reaction formation the second heavy network that simultaneously occurs in monomer polymerization process the amount of two networks is accurately controlled; Prepared high intensity hydrogel has the feature of high-intensity high-tenacity, its tensile strength of gel is that 0.6-1.2 MPa, tensile modulus are that 100-200 KPa, tension strain reach 1000-2680%, compressive strength is that 30-40 MPa, modulus of compression are that 100-200 KPa, compressive strain are greater than 95%, and toughness reaches 10
2-10
4j/m
2;prepared high intensity hydrogel can be widely used in tissue repair, artificial organ, medicament slow release, sensor numerous areas.
Accompanying drawing explanation
Fig. 1 is that the material object of the high intensity hydrogel of the embodiment of the present invention 1 can carry out bending photo in kind;
Fig. 2 is the photo in kind that the high intensity hydrogel of the embodiment of the present invention 1 can be tied a knot;
Fig. 3 is the photo in kind that can compress of the high intensity hydrogel of the embodiment of the present invention 1;
Fig. 4 is the photo in kind that the high intensity hydrogel of the embodiment of the present invention 1 can stretch;
Fig. 5 is the stress-strain curve of the stretching experiment of the high intensity hydrogel of the embodiment of the present invention 1, and in figure, a is the stress-strain curve of the high intensity hydrogel of embodiment 1, the stress-strain curve that b is polyacrylamide hydrophilic gel.
Embodiment
A kind of high intensity hydrogel is double-network hydrogel or interpenetration network hydrogel; Its tensile strength is that 1.0 MPa, tensile modulus are that 100-200 KPa, tension strain reach 1000-2500%, and compressive strength is that 30-40 MPa, modulus of compression are that 100-200 KPa, compressive strain are greater than 95%, and toughness reaches 10
2-10
4j/m
2.
A kind of preparation method of high intensity hydrogel, its concrete preparation method is, described high intensity hydrogel adopts the method for " treating different things alike ", be about to hydrogel and prepare the required polymkeric substance that weighs network in order to form first of dual network gel, in order to polymerization, form the monomer of the second heavy network of double-network hydrogel, in order to the initiator of trigger monomer polymerization, thereby with forming the direct disposable mixing such as the linking agent of the second heavy network and water so that there is crosslinking reaction in monomer polymerization process simultaneously, by certain incentive condition, all substances are dissolved and form homogeneous phase solution, then reusable heat or light initiation polymerization just obtain high intensity hydrogel,
Described is one or more the combination in agar, agarose, gelatin, collagen protein, scleroproein, alginates, hyaluronate, chondroitin sulfate, carrageenin, gellan gum, guar gum, sesbania gum, chitosan, Sumstar 190 in order to form the polymkeric substance of the first heavy network of dual network gel;
The monomer of described the second heavy network in order to polymerization formation double-network hydrogel is acrylamide, N, the combination of one or more in N'-DMAA, vinylformic acid and salt thereof, methacrylic acid and salt thereof, stearyl methacrylate, methacrylic acid laurate, polyethyleneglycol diacrylate;
The described initiator in order to trigger monomer polymerization is 2,2-diethoxy acetophenone, 2-hydroxyl-4'-(2-hydroxy ethoxy) one in-2-methyl phenyl ketone, 1-hydroxy-cyclohexyl Propiophenone, 2-oxopentanedioic acid, Ammonium Persulfate 98.5, Potassium Persulphate;
Thereby described use is so that the linking agent that crosslinking reaction forms the second heavy network occurs in monomer polymerization process is N simultaneously, the one in N'-methylene-bisacrylamide, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), polyethyleneglycol diacrylate;
Described certain incentive condition is heating, illumination, pH.
A preparation method for high intensity hydrogel, the preferred following scheme of its preparation method; Concrete preparation process is:
Rapid one, take polymkeric substance, monomer, initiator, linking agent, other additives and water in reactor, the concentration that makes polymkeric substance is that 1-100 mg/mL, monomer concentration are that 1-5 mol/L, initiator are that 0.01-5 mol%, linking agent are that then 0-5 mol% goes out the oxygen in reactor by nitrogen or argon replaces for the volumetric molar concentration per-cent of monomer with respect to the volumetric molar concentration per-cent of monomer, obtains mixed reaction solution;
Step 2, the mixed reaction solution in reactor is stirred at 60-90 ℃ to 5-10 min and make it form homogeneous phase transparent settled solution; Transparent gained settled solution irradiation 1-2 h under the ultraviolet lamp of 365 nm is made to high intensity hydrogel.
In the time of can being chosen in mixing water gel in its preparation method and preparing required each material, add supplementary additive, described supplementary additive is one or more the combination in tensio-active agent, divalent metal, trivalent metal cation, small molecule salt; Described tensio-active agent is sodium laurylsulfonate, sodium lauryl sulphate or cetyl trimethylammonium bromide; Described divalent metal is Ca
2+, Cu
2+, Zn
2+, Co
2+, Sr
2+or Ba
2+; Described trivalent metal cation is Fe
3+, Al
3+or Eu
3+; Described small molecule salt is NaCl or NaSCN; The total amount of adding is 0-5 mol/L.
By 20 mg agar, 2400 mg acrylamides, 0.0575 g 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 78 μ L N, after N'-methylene-bisacrylamide solution (20 mg/mL) accurate weighing, join in reactor, then add 10 mL deionized waters.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 90 ~ 95
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to room temperature and form agar gel.Above-mentioned agar gel just can be obtained under the UV-light of 365 nm to high intensity hydrogel as shown in Figure 1,2,3, 4 (gel can be bending, knotting, compression and stretch and do not rupture) after initiated polymerization 1 h.The stress-strain curve of agar/polyacrylamide high intensity hydrogel (Agar/PAM DN gel) tension test as shown in Figure 5, the stress-strain curve of the high intensity hydrogel that in figure, a is the present embodiment, the stress-strain curve that b is polyacrylamide hydrophilic gel; The tensile strength of the high intensity hydrogel of the present embodiment is that 1 MPa, tensile modulus are that 120 KPa, elongation at break reach 2000%, and the mechanical property of gel is obviously better than the physical strength of polyacrylamide hydrophilic gel (PAM gel).
embodiment 2
By 50 mg gelatin, 2000 mg acrylamides, 29 μ L N, after N'-methylene-bisacrylamide solution (20 mg/mL) accurate weighing, join in reactor, then add 10 mL deionized waters.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 60
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, solution are poured in reaction mould after adding 120 μ L persulfuric acid acid ammoniums or persulfate aqueous solution (20 mg/mL), make it 60
oc reacts after 2 h again 4
ocooling 0.5 h of C.Tensile strength is 1.2 MPa, tensile modulus 146 KPa, elongation at break 1740%, compressive strength approximately 40 MPa, modulus of compression approximately 155 KPa, compressive strain 96%, and the toughness of gel reaches 800 J/m
2.
embodiment 3
By joining in reactor after 10 mg collagen proteins, 10 mg agaroses, 2400 mg acrylamides, 0.0575 g 2-oxopentanedioic acid, 78 μ L ethylene glycol dimethacrylate solution (20 mg/mL) accurate weighings, then add the 10 mL 0.5 mol/L NaCl aqueous solution.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 80
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to gel formed at room temperature.Above-mentioned gel is just formed to high intensity hydrogel after initiated polymerization 1 h under the UV-light of 365 nm, tensile strength is 1.2 MPa, tensile modulus 126 KPa, elongation at break 1800%, the about 35MPa of compressive strength, modulus of compression approximately 130 KPa, compressive strain 97%, the toughness of gel reaches 1000 J/m
2.
embodiment 4
By 20 mg scleroproeins, 10 mg sodium alginates, 2400 mg acrylamides, 0.0575 g 2,2-diethoxy acetophenone, 26 μ L N, after N'-methylene-bisacrylamide solution (20 mg/mL) accurate weighing, join in reactor, then add 10 mL deionized waters.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 90
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to room temperature, then under the UV-light of 365 nm, after initiated polymerization 1 h, just can obtain high intensity hydrogel.Tensile strength ~ 0.8 MPa, tensile modulus 96 KPa, elongation at break 1680%, compressive strength approximately 25 MPa, modulus of compression approximately 104 KPa, compressive strain 96%, the toughness of gel reaches 500 J/m
2.
embodiment 5
By 10 mg gelatin, 10 mg carrageenins, 10 mg hyaluronate sodiums, 2400 mg N, after N'-DMAA, 0.0575 g 1-hydroxy-cyclohexyl Propiophenone, 50 μ L polyethyleneglycol diacrylate solution (20 mg/mL) accurate weighings, join in reactor, then add 10 mL 0.5 mol/L CaCl
2solution.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 60
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to room temperature, then under the UV-light of 365 nm, after initiated polymerization 1 h, just can obtain high intensity hydrogel.Tensile strength is 1.2 MPa, tensile modulus 136 KPa, elongation at break 2300%, compressive strength approximately 44 MPa, modulus of compression approximately 143 KPa, compressive strain 96%, and the toughness of gel reaches 1200 J/m
2.
embodiment 6
To after 20 mg agar, 1800 mg acrylamides, 200 mg stearyl methacrylates, 0.0575 g 2-oxopentanedioic acid accurate weighing, join in reactor, then add 10 mL 7% w/v CTAB/SDS solution (wherein CTAB/SDS=4/1 contains 0.5 mol/L NaSCN in solution).Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 90
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to room temperature, then under the UV-light of 365 nm, after initiated polymerization 1 h, just can obtain high intensity hydrogel.Tensile strength is 0.78 MPa, tensile modulus 116 KPa, elongation at break 2170%, compressive strength approximately 18 MPa, modulus of compression approximately 125 KPa, compressive strain 98%, and the toughness of gel reaches 300 J/m
2.
embodiment 7
By 50 mg gelatin, 1800 mg acrylamides, 200 mg methacrylic acid laurates, 0.0575 g 2-oxopentanedioic acid, after 50 μ L diethyleneglycol dimethacrylate(DEGDMA) solution (20 mg/mL) accurate weighings, join in reactor, then add 10 mL 7% w/v SDS solution (wherein containing 0.5 mol/L NaCl).Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 60
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to room temperature, then under the UV-light of 365 nm, after initiated polymerization 1 h, just can obtain high intensity hydrogel.Tensile strength is 0.65 MPa, tensile modulus 98 KPa, elongation at break 1850%, and compressive strength approximately 17 MPa, modulus of compression approximately 110 KPa, compressive strain are 97%, and the toughness of gel reaches 300 J/m
2.
embodiment 8
By joining in reactor after 20 mg gelatin, 10 mg hyaluronate sodiums, 10 mg chondroitin sulfates, 2500 mg vinylformic acid, 0.0575 g 2-oxopentanedioic acid, 50 μ L polyethyleneglycol diacrylate solution (20 mg/mL) accurate weighings, then add 10 mL 0.5 mol/L ZnCl
2solution.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 60
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, solution are poured in reaction mould after adding 120 μ L persulfuric acid acid aqueous solutions of potassium (20 mg/mL), make it 60
oc reacts after 2 h again 4
ocooling 0.5 h of C.Tensile strength is 1.0 MPa, tensile modulus 92 KPa, elongation at break 1500%, and compressive strength approximately 36 MPa, modulus of compression approximately 110 KPa, compressive strain are 95%, and the toughness of gel reaches 800 J/m
2.
embodiment 9
By 10 mg agar, 20 mg sodium alginates, 20 mg gellan gums, 2400 mg acrylamides, 0.0575 g 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 26 μ L N, after N'-methylene-bisacrylamide solution (20 mg/mL) accurate weighing, join in reactor, then add 10 mL 0.5 mol/L FeCl
3or Al
2(SO
4)
3solution.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 90
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to room temperature, then under the UV-light of 365 nm, after initiated polymerization 1 h, just can obtain high intensity hydrogel.Tensile strength ~ 0.60 MPa, tensile modulus 86 KPa, elongation at break 2680%, compressive strength approximately 15 MPa, modulus of compression approximately 96 KPa, compressive strain are greater than 95%, and the toughness of gel reaches 9000 J/m
2.
Embodiment 10: by joining in reactor after 10 mg gelatin, 10 mg agar, 2000 mg polyethyleneglycol diacrylates, 0.0575 g 2-oxopentanedioic acid, 120 μ L diethyleneglycol dimethacrylate(DEGDMA) (20 mg/mL) accurate weighings, then add 10 mL deionized waters.Circulation deoxygenation after reaction solution sealing is rushed to nitrogen three times, 80
oin the oil bath of C or water-bath, heated and stirred 5 ~ 10 min make it to form homogeneous phase transparent settled solution, then solution are poured in reaction mould, make it to be cooled to gel formed at room temperature.Above-mentioned gel is just formed to high intensity hydrogel after initiated polymerization 1 h under the UV-light of 365 nm, tensile strength is 0.9 MPa, tensile modulus 110 KPa, elongation at break 2100%, compressive strength approximately 36 MPa, modulus of compression approximately 120 KPa, compressive strain are 96%, and the toughness of gel reaches 2600 J/m
2.
Claims (3)
1. the preparation method of a high intensity hydrogel, it is characterized in that: its concrete preparation method is, hydrogel is prepared to the required polymkeric substance that weighs network in order to form first of dual network gel, in order to polymerization, form the monomer of the second heavy network of double-network hydrogel, in order to the initiator of trigger monomer polymerization, thereby with forming the second heavily linking agent and direct disposable mixing of water of network so that there is crosslinking reaction in monomer polymerization process simultaneously, by certain incentive condition, all substances are dissolved and form homogeneous phase solution, then reusable heat or light initiation polymerization just obtain high intensity hydrogel,
Described is one or more the combination in agar, agarose, gelatin, collagen protein, scleroproein, alginates, hyaluronate, chondroitin sulfate, carrageenin, gellan gum, guar gum, sesbania gum, chitosan, Sumstar 190 in order to form the polymkeric substance of the first heavy network of dual network gel;
The monomer of described the second heavy network in order to polymerization formation double-network hydrogel is acrylamide, N, the combination of one or more in N'-DMAA, vinylformic acid and salt thereof, methacrylic acid and salt thereof, stearyl methacrylate, methacrylic acid laurate, polyethyleneglycol diacrylate;
The described initiator in order to trigger monomer polymerization is 2,2-diethoxy acetophenone, 2-hydroxyl-4'-(2-hydroxy ethoxy) one in-2-methyl phenyl ketone, 1-hydroxy-cyclohexyl Propiophenone, 2-oxopentanedioic acid, Ammonium Persulfate 98.5, Potassium Persulphate;
Thereby described use is so that the linking agent that crosslinking reaction forms the second heavy network occurs in monomer polymerization process is N simultaneously, the one in N'-methylene-bisacrylamide, ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), polyethyleneglycol diacrylate;
Described certain incentive condition is heating, illumination, pH.
2. the preparation method of high intensity hydrogel as claimed in claim 1, is characterized in that: its concrete preparation process is:
Step 1, take polymkeric substance, monomer, initiator, linking agent and water in reactor, the concentration that makes polymkeric substance in reactor is that 1-100 mg/mL, monomer concentration are that 1-5 mol/L, initiator are that 0.01-5 mol%, linking agent are 0-5 mol% for the volumetric molar concentration per-cent of monomer with respect to the volumetric molar concentration per-cent of monomer, then by nitrogen or argon replaces, goes out the oxygen in reactor;
Step 2, the mixed reaction solution in reactor is stirred at 60-90 ℃ to 5-10 min, make it form homogeneous phase transparent settled solution; Transparent gained settled solution irradiation 1-2 h under the ultraviolet lamp of 365 nm is made to high intensity hydrogel.
3. as the preparation method of the high intensity hydrogel of claim 1-2 as described in one of them, it is characterized in that: when mixing water gel is prepared required each material, add supplementary additive; Described supplementary additive is one or more the combination in tensio-active agent, divalent metal, trivalent metal cation, small molecule salt; Described tensio-active agent is sodium laurylsulfonate, sodium lauryl sulphate or cetyl trimethylammonium bromide; Described divalent metal is Ca
2+, Cu
2+, Zn2+, Co
2+, Sr
2+or Ba
2+; Described trivalent metal cation is Fe
3+, Al
3+or Eu
3+; Described small molecule salt is NaCl or NaSCN; The total amount of adding is 0-5 mol/L.
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