CN104804115A - High-strength supramolecular hydrogel and preparation method and application thereof - Google Patents

High-strength supramolecular hydrogel and preparation method and application thereof Download PDF

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CN104804115A
CN104804115A CN201510191607.7A CN201510191607A CN104804115A CN 104804115 A CN104804115 A CN 104804115A CN 201510191607 A CN201510191607 A CN 201510191607A CN 104804115 A CN104804115 A CN 104804115A
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hydrogel
monomer
high strength
initiator
supramolecular hydrogel
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CN104804115B (en
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刘文广
戴西洋
张银宇
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/36—Amides or imides
    • C08F122/38—Amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
    • A61L27/38—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix containing added animal cells
    • A61L27/3804—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix containing added animal cells characterised by specific cells or progenitors thereof, e.g. fibroblasts, connective tissue cells, kidney cells
    • A61L27/3817—Cartilage-forming cells, e.g. pre-chondrocytes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52—Hydrogels or hydrocolloids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers

Abstract

The invention discloses a high-strength supramolecular hydrogel and a preparation method and application thereof. The high-strength supramolecular hydrogel is prepared by using acryloyl glycinamide as a monomer and triggering in the presence of an initiator; because of the synergistic effect of hydrogen bonds, the supramolecular hydrogel is high in tensile strength and anti-tear while being compressed, can realize functions of thermoplasticity and self-repair at a high temperature, and is good in biocompatibility.

Description

A kind of high strength supramolecular hydrogel and its preparation method and application
Technical field
The present invention relates to a kind of hydrogel and preparation method; more particularly; relate to a kind of PNAGA hydrogel of preparing for monomer with acryl G-NH2 (NAGA) and preparation method, there is the function of high stability, high strength, thermoplasticity and selfreparing.
Background technology
Hydrogel take water as dispersion medium, wetting ability and water-fast and can absorb the macromolecule polymer material that large quantity of moisture (usual water content is greater than 50% of total mass) has crosslinking structure.Because the physical crosslinking between polymer chain and chemically crosslinked effect and can not be dissolved in the water, can only be swelling and keep certain shape, meanwhile, also there is good water permeate, biocompatibility, can untoward reaction be reduced as body implant.Thus hydrogel is used widely as excellent bio-medical material.But, the mechanical property that its high-moisture causes hydrogel poor limits its application as biomaterial especially mechanics device, all the more so for supramolecular hydrogel, especially the effect of chemical bond is not had, the supramolecular hydrogel mechanical strength of physical crosslinking is in general all more weak, and therefore the supramolecular hydrogel of preparation preparation high strength has very large reality and theoretical application.
In order to solve this problem of the poor mechanical property of hydrogel, recent scientists have developed following several high intensity hydrogel: dual network (DN) hydrogel, intercalated inorganic Nanometer composite hydrogel (NC) and polymer microsphere composite aquogel (MMC).But these high intensity hydrogels do not have high stretch-proof and incompressible function (Yoshimi Tanaka concurrently, JainPing Gong, Yoshihito Osada.Novel hydrogels with excellent mechanical performance. (MMC).But these high intensity hydrogels do not have high stretch-proof and incompressible function (Yoshimi Tanaka concurrently, JainPing Gong, Yoshihito Osada.Novel hydrogels with excellent mechanical performance.Prog.Polym.Sci.2005; 30:1-9.).Only make high intensity hydrogel by pure physical crosslinking effect.There are (the Sun T L such as Gong recently, Kurokawa T, Kuroda S, et al.Physical hydrogels composed of polyampholytesdemonstrate high toughness and viscoelasticity.Nat.Mater.2013; 12:932-937.) scholar's pure physics high intensity hydrogel of utilizing polyelectrolyte to make, but its water content only has 50%, and polypropylene acyl group G-NH2 gel not only has the high strength on mechanics, and possess thermoplasticity and self-repair function.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art; a kind of polymer supermolecule hydrogel being only monomer with acryl G-NH2 (NAGA) is provided; this supermolecule polymer hydrogel is except showing some build-in attributes of hydrogel; also there is very strong stretching, Compressive Mechanical Properties, the thermoplasticity under good tear strength, temperature-responsive and self-repair function.
Technical purpose of the present invention is achieved by following technical proposals:
A kind of high strength supramolecular hydrogel, be made up of the polymkeric substance being monomer with acryl G-NH2 and water, the water content of hydrogel is 55-85%; in the polymer; the side chain of each repeating unit is provided with two amide groups, and the polymerization degree is 1000-5000, and preferably 2000-4000.
In above-mentioned hydrogel, water content and the polymerization degree present inversely prroportional relationship, and namely water content declines along with the increase of acryl G-NH2 monomer consumption.
The preparation method of above-mentioned hydrogel, carries out according to following step: be that monomer dissolves under aqueous phase condition by acryl G-NH2, add initiator, under anoxic condition, carry out radical polymerization by the carbon-carbon double bond of initiator initiation acryl G-NH2.
In above-mentioned preparation method, described aqueous phase selects deionized water, or tap water.
In above-mentioned preparation method, the consumption of described initiator is 3%-5% of monomer propylene acyl group G-NH2 quality.
In above-mentioned preparation method, the concentration of described monomer propylene acyl group G-NH2 is 10-60%, i.e. quality/(quality of the quality+aqueous phase of acrylamido G-NH2 monomer) of acrylamido G-NH2 monomer.
The free radical utilizing initiator to provide causes NAGA monomer and reacts.Wherein initiator can to select in field of macromolecule polymerization the thermal initiator under conventional aqueous phase condition, as ammonium persulphate (APS), Potassium Persulphate (KPS), or light trigger, as 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure 1173).If selection thermal initiator, then need first to utilize rare gas element (as nitrogen, argon gas or helium) to get rid of oxygen in reaction system, to avoid its inhibition, then according to activity and the consumption of initiator, keep considerable time on kick off temperature reaction system being heated to initiator used, as more than 1h or longer (1-5h), abundant free radical can be produced for a long time to impel initiator, initiation reaction system continues Raolical polymerizable occurs, final preparation hydrogel of the present invention.If selective light initiator, wherein initiator have selected light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure 1173).Transparent airtight reaction vessel can have been selected, radical polymerization is caused under the condition of UV-irradiation, because light-initiated efficiency is higher than thermal initiation, because of during according to the activity of selected initiator and consumption adjustment irradiation time, irradiation time can be shorter than the heat-up time of thermal initiation, as 20 minutes or longer (30min-1h), experimental period can be made like this to greatly reduce relative to thermal initiation.
In preparation scheme, after the completion of reaction, from reaction vessel, multipolymer is taken out, after removing monomer, initiator, linking agent and the solvent not participating in reaction, be immersed in water until reach swelling equilibrium (as soaked 7 days, changing a water every 12h, reaching swelling equilibrium).In the inventive solutions, with acryl G-NH2 (NAGA) for monomer, the hydrogel of preparation, with two amide groups on the side chain of its molecular chain, intermolecular intermolecular hydrogen bond action strongly, (-CH 2-CH 2-) n" carbon-to-carbon " singly-bound be connected skeleton structure, the amide group of side chain (CO-NH).Acryl G-NH2 makes initiator provide free radical under the condition of initiator; acryl G-NH2 (NAGA) double bond is caused again by free radical; polymerization reaction take place; in the hydrogel material of final preparation; due to the synergy of hydrogen bond, whole hydrogel material is made up of polymkeric substance and water.
Compared with prior art; acryl G-NH2 (NAGA) in the present invention; due on the side chain of its polymer molecular chain with two amide groups; intermolecular intermolecular hydrogen bond action strongly; thus the physical crosslinking effect formed makes acryl G-NH2 gel have good mechanical strength and toughness; and because this hydrogen bond formed by bisamide group can realize destroying and rebuilding at relatively high temperatures, gel is provided with the function of thermoplasticity and selfreparing.A kind of high strength PNAGA hydrogel provided by the invention is for raw material with acryl G-NH2 (NAGA); cause under initiator exists and be prepared from; due to the synergy of hydrogen bond; can anti tear while this hydrogel has very strong stretching, compression; the function of thermoplasticity and selfreparing can be realized at higher temperatures, and good biocompatibility.
Accompanying drawing explanation
Fig. 1 is the FTIR spectrum figure of the monomer propylene acyl group G-NH2 that the present embodiment uses.
Fig. 2 is the FTIR spectrum figure of the acryl G-NH2 polymkeric substance of the present embodiment synthesis.
Fig. 3 is the stretching of the polypropylene acyl group G-NH2 hydrogel that the present invention synthesizes, compression and knotting pictorial diagram, and wherein 1 is knotting, 2 stretchings, 3 compressions.
Fig. 4 is the process schematic of the remoldability of polypropylene acyl group G-NH2 hydrogel of the present invention at 50 DEG C-90 DEG C.
Fig. 5 is the schematic diagram that polypropylene acyl group G-NH2 hydrogel of the present invention realizes selfreparing when cutting in half at 50-90 DEG C.
Fig. 6 is polypropylene acyl group G-NH2 hydrogel PNAGA-25 of the present invention and the stability test of polyacrylamide hydrophilic gel in water and in urea; a be polyacrylamide hydrophilic gel in deionized water; b be PNAGA-25 hydrogel in deionized water, c is that PNAGA-25 hydrogel is at 5mol L -1aqueous solution of urea in.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.
In an embodiment; with glycyl amide hydrochloride and acrylate chloride for raw material is according to reference (Boustta M; Colombo P E; Lenglet S; et al.Versatile UCST-based thermoresponsive hydrogels forloco-regional sustained drug delivery [J] .Journal of Controlled Release; 2014; 174:1-6) prepare a kind of monomer propylene acyl group G-NH2 with two amide groups, shown in the following chemical formula of chemical formula structure:
Utilize FTIR spectrum (platinum Elmer Co., Ltd of the U.S.) to demonstrate it successfully to synthesize, wherein their characteristic peak is as follows: ν=3389cm -1(m, NH), 3314cm -1(s, NH), 3191cm -1(m, NH), 1662cm -1(vs, C=O), 1626cm -1(vs, C=O), 1556cm -1(vs, NH) (referring to accompanying drawing 1).
With the acryl G-NH2 of above-mentioned synthesis for monomer carries out homopolymerization; select aqueous phase (such as ordinary tap water, deionized water) for polymerization environment; simultaneously for polymkeric substance provides water surrounding; water soluble starter selected by initiator; the polyacrylamide base G-NH2 gel of synthesis different monomers concentration; for monomer concentration for 25%, i.e. quality/(quality of the quality+water of acrylamido G-NH2 monomer) of acrylamido G-NH2 monomer.
By acrylamido G-NH2 monomer (243mg), after the deionized water of 750 μ L dissolves completely, add light trigger Irgacure 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) 7 μ L.Mixed solution, after inflated with nitrogen deoxygenation, is injected airtight mould by mixed solution, and mould irradiates 40 minutes to ensure fully to cause radical polymerization in ultra-violet curing case.Open mould subsequently and take out gel, soak several days at deionized water, reach swelling equilibrium, change above-mentioned deionized water every 12h.The homopolymer of FTIR spectrum (platinum Elmer Co., Ltd of the U.S.) to synthesis is utilized to carry out Infrared Characterization, specifically as shown in Figure 2, the characteristic peak that basic expressions is identical with accompanying drawing 1, this illustrates that in acrylamido G-NH2 monomer, carbon-carbon double bond carries out opening and being polymerized, and all the other structures there is no and change.
Prepare the gel of different monomers concentration by same steps, carry out the experimentations such as mechanical property, tear resistance, thermoplasticity and selfreparing.This gel sample called after PNAGA-X, wherein X representative is the monomer concentration of gel.Change the concentration of monomeric acrylamide base G-NH2 monomer, the consumption of light trigger Irgacure 1173 is 3% of monomer mass, is prepared as follows hydrogel sample PNAGA-10, PNAGA-15, the supermolecule polymer hydrogel of the different concns of PNAGA-20, PNAGA-25, PNAGA-30.
Adopt the Mechanics Performance Testing testing polyacrylamide base G-NH2 hydrogel of the present invention with the following method carrying out on electronic universal tester (Jinan epoch company limited), the sample of stretching mechanical property testing is of a size of 20mm × 10mm, thick is 500 μm, and rate of extension is 50mm/min; The sample size of Compressive Mechanical Properties test is the cylinder of diameter 10mm, high 8mm, and compression speed is 10mm/min.Be of a size of 20mm × 10mm at the sample carrying out stretching mechanical property testing, thick is 500 μm.The sample size of Compressive Mechanical Properties test is the cylinder of diameter 10mm, high 8mm.Tear resistance test sample size is according to 1/2GBT 529-2008A size (wide 7.5mm, long 50mm, notch length 20mm, thickness 0.5mm).The tensile strength of this supramolecular hydrogel, compressive strength can both reach the rank of MPa.Table 1 is the various performance parameters of hydrogel sample:
Compressive strength: during measurement, gel is compressed to machine maximum range and also cannot compresses, so using the stress of 90% strain place as intensity.PNAGA-x:x represents the massfraction of polymerization single polymerization monomer, i.e. quality/(quality of the quality+water of acrylamido G-NH2 monomer) of acrylamido G-NH2 monomer.Change the massfraction to 50%, 60% of polymerization single polymerization monomer, polymkeric substance all shows the character with above-mentioned list basic simlarity, namely in the homopolymer hydrogel of one-component, tensile strength, compressive strength can both reach MPa rank, and knotting, Tension and Compression behavior can be made with hydrogel material object, as shown in Figure 3.
Use ten thousand/ electronic scales carry out the test of hydrogel water content, first the weight in wet base of hydrogel is taken, then hydrogel is added heat abstraction moisture under constant temperature (50 degrees Celsius) condition, to constant weight, take the dry weight of hydrogel again, utilize (hydrogel wet-hydrogel dry)/hydrogel wet * 100%, hydrogel water content can be obtained.PNAGA-x:x represents the massfraction of polymerization single polymerization monomer, i.e. quality/(quality of the quality+water of acrylamido G-NH2 monomer) of acrylamido G-NH2 monomer, and change x and rise to 60% by 10%, water content drops to 55% by 85%.Through the molecular weight of GPC chromatographic determination polymkeric substance, the corresponding acryl G-NH2 polymerization degree is 1000-5000.
Profit detects the thermoplasticity of polyacrylamide base G-NH2 hydrogel of the present invention with the following method, by the hydrogel fragment prepared, put into a difform encloses container, heat at the temperature of 50 DEG C-90 DEG C after 30 minutes, its self-heating is allowed to be cooled to room temperature 20-25 degrees Celsius, finally demould can prepare difform polyacrylamide base G-NH2 hydrogel (referring to Figure of description 4), this process can repeat, realize recycling, be expected to alleviate environmental pressure, i.e. polyacrylamide base G-NH2 hydrogel of the present invention, as the application of thermoplastic polymer, processing temperature is 50 DEG C-90 DEG C.
Profit detects the self-repair function of polyacrylamide base G-NH2 hydrogel of the present invention with the following method.The hydrogel of preparation is cut in half, wherein half chemical reagent rhodamine B carries out dyeing so that distinguish, then by cut two semi-gelleds to upper, namely two half block hydrogels come in contact, put into sealed vessel to heat 1 hour at the temperature of 50 DEG C-90 DEG C, the gel finally cut can be bonded together well, and can't see interface, refer to Figure of description 5, illustrate that two blocks of hydrogels complete self-regeneration, i.e. polyacrylamide base G-NH2 hydrogel of the present invention, as the application of self-repair material, repairing temperature is 50 DEG C-90 DEG C.
Profit detects the cytotoxicity of polyacrylamide base G-NH2 hydrogel of the present invention with the following method.Biomaterial possibility is applied in order to test this high strength supramolecular hydrogel.It is 10.2mm that gel film of the present invention is cut into diameter, soaks 2h and make it sterilize in the alcohol (aqueous ethanolic solution) of percent by volume 75%, and then with PBS washing, the bottom of 48 orifice plates put into by these gels.By the chondrocyte ATDCA5 suspension (5 × 10 of 2mL 4cells/mL) plant in 48 orifice plates, cultivate 24 hours.Fluorexon is added in the CO of 37 DEG C and 5% subsequently 2cultivate 30 minutes under environment, the exciting light of fluorescence 490nm and the utilizing emitted light of 520nm are recorded.Detect that cell survival rate reaches more than 90%, do not find significant cytotoxicity, experimental result indicates this gel and has good biocompatibility, can as the application of the biomaterials such as cytoskeleton, such as, as the timbering material of cultured cartilage cell ATDCA5.
Prior art often uses acrylamide gel hydrogel, selects polyacrylamide base G-NH2 hydrogel of the present invention, contrasts with it.With polypropylene acyl group G-NH2 hydrogel PNAGA-25, same process and the polyacrylamide hydrophilic gel of only replacing homopolymerization monomer of filling a prescription is adopted to be example with PNAGA-25.As shown in Figure 6; polypropylene acyl group G-NH2 hydrogel PNAGA-25 of the present invention and the stability test of polyacrylamide hydrophilic gel in water and in urea; a be polyacrylamide hydrophilic gel in deionized water; b be PNAGA-25 hydrogel in deionized water, c is that PNAGA-25 hydrogel is at 5mol L -1aqueous solution of urea in.Experiment shows that this polyacrylamide base G-NH2 hydrogel with bisamide group has good stability, and this stability produces due to the synergy of amide group hydrogen bond, the polyacrylamide base G-NH2 hydrogel with two amide group of the present invention has more excellent performance than the acrylamide gel only with an amide group.Utilize identical method to prepare acrylamide gel, this gel-strength is too low, can not be referred to as high intensity hydrogel, can disintegrate completely after in addition acrylamide gel being put into deionized water for some time; And can very stably there is some months with the polyacrylamide base G-NH2 hydrogel of two amide group and do not change.
In the monomer amount ranges of technical solution of the present invention, the processing parameters such as adjustment initiator type/consumption, reaction times and temperature of reaction, the character that the hydrogel of final preparation and above-described embodiment are listed is consistent substantially.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.

Claims (10)

1. a high strength supramolecular hydrogel, is characterized in that, is made up of the polymkeric substance being monomer with acryl G-NH2 and water; the water content of hydrogel is 55-85%; in the polymer, the side chain of each repeating unit is provided with two amide groups, and the polymerization degree is 1000-5000.
2. a kind of high strength supramolecular hydrogel according to claim 1, is characterized in that, polymkeric substance preferably 2000-4000.
3. a kind of high strength supramolecular hydrogel according to claim 1, it is characterized in that, water content and the polymerization degree present inversely prroportional relationship, and namely water content declines along with the increase of acryl G-NH2 monomer consumption.
4. the preparation method of a high strength supramolecular hydrogel, it is characterized in that, carry out according to following step: be that monomer dissolves under aqueous phase condition by acryl G-NH2, add initiator, under anoxic condition, carry out radical polymerization by the carbon-carbon double bond of initiator initiation acryl G-NH2; Described aqueous phase selects deionized water, or tap water; The consumption of described initiator is 3%-5% of monomer propylene acyl group G-NH2 quality; The concentration of described monomer propylene acyl group G-NH2 is 10-60%, i.e. quality/(quality of the quality+aqueous phase of acrylamido G-NH2 monomer) of acrylamido G-NH2 monomer.
5. the preparation method of a kind of high strength supramolecular hydrogel according to claim 4, is characterized in that, described initiator is ammonium persulphate, persulfuric acid, or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
6. the preparation method of a kind of high strength supramolecular hydrogel according to claim 4, it is characterized in that, select thermal initiator, then need first to utilize the oxygen in rare gas element eliminating reaction system, to avoid its inhibition, then according to activity and the consumption of initiator, 1-5h is kept on kick off temperature reaction system being heated to initiator used.
7. the preparation method of a kind of high strength supramolecular hydrogel according to claim 4, is characterized in that selective light initiator causes radical polymerization under the condition of UV-irradiation, and irradiation time is 20 minutes or 30min-1h.
8. the high strength supramolecular hydrogel as described in one of claim 1-3, as the application of thermoplastic polymer, processing temperature is 50 DEG C-90 DEG C.
9. the high strength supramolecular hydrogel as described in one of claim 1-3 is as the application of self-repair material, and repairing temperature is 50 DEG C-90 DEG C.
10. the high strength supramolecular hydrogel as described in one of claim 1-3, as the application of the biomaterials such as cytoskeleton, as the timbering material of cultured cartilage cell ATDCA5.
CN201510191607.7A 2015-04-21 2015-04-21 High-strength supramolecular hydrogel and preparation method and application thereof Expired - Fee Related CN104804115B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201610702465.0A CN106336474B (en) 2015-04-21 2015-04-21 Application of the high intensity hydrogel based on acryloyl group glycine amide as thermoplastic polymer
CN201510191607.7A CN104804115B (en) 2015-04-21 2015-04-21 High-strength supramolecular hydrogel and preparation method and application thereof
CN201610702561.5A CN106349412B (en) 2015-04-21 2015-04-21 Application of the supramolecular hydrogel based on acryloyl group glycine amide as self-repair material

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Publication number Priority date Publication date Assignee Title
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030186293A1 (en) * 2000-08-21 2003-10-02 Noriyuki Ohnishi Polymers
CN104031261A (en) * 2014-06-20 2014-09-10 电子科技大学 Thermosensitive copolymer and hydrogel system thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2987272B1 (en) * 2012-02-27 2014-03-28 Centre Nat Rech Scient ASSOCIATION OF POLY (N ACRYLOYL GLYCINAMIDE) WITH AT LEAST ONE ACTIVE INGREDIENT.
CN104987471B (en) * 2013-10-11 2017-09-19 天津大学 The preparation method of high-strength light sensitive aquagel
CN104387538B (en) * 2014-11-20 2017-03-08 天津大学 There is high-strength shape memory hydrogel of anti tear and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030186293A1 (en) * 2000-08-21 2003-10-02 Noriyuki Ohnishi Polymers
CN104031261A (en) * 2014-06-20 2014-09-10 电子科技大学 Thermosensitive copolymer and hydrogel system thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAHFOUD BOUSTTA ET.AL: "Versatile UCST-based thermoresponsive hydrogels for loco-regional sustained drug delivery", 《JOURNAL OF CONTROLLED RELEASE》 *

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