CN102226007B - Double network polymer hydrogel and preparation method thereof - Google Patents

Double network polymer hydrogel and preparation method thereof Download PDF

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CN102226007B
CN102226007B CN201110092271A CN201110092271A CN102226007B CN 102226007 B CN102226007 B CN 102226007B CN 201110092271 A CN201110092271 A CN 201110092271A CN 201110092271 A CN201110092271 A CN 201110092271A CN 102226007 B CN102226007 B CN 102226007B
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polyoxyethylene glycol
hydrogel
dual network
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polyalcohol hydrogel
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CN102226007A (en
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戴李宗
邓胡军
陈光剑
郭一宾
许一婷
罗伟昂
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Xiamen University
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Abstract

A double network polymer hydrogel and a preparation method thereof provided in the invention, relate to a biomedical material. The polymer hydrogel comprises the following ingredients: 60-90wt% of polyethylene glycol maleic anhydride diester and N-isopropyl acrylamide or acrylamide copolymer, and 10-40wt% of N-isopropyl acrylamide or acrylamide homopolymer. The preparation method comprises the following two steps: first, utilizing an esterification reaction between polyethylene glycol PEG and maleic anhydride to obtain polyethylene glycol maleic anhydride diester with carboxyl as end group, then carrying out in situ polymerization, chemical crosslinking or UV photo-initiation crosslinking between polyethylene glycol maleic anhydride diester and a functional monomer such as N-isopropyl acrylamide or acrylamide and the like to form a soft network micro-area by the copolymer and form a hard network framework by the homopolymer of the functional monomer, so as to obtain the double network polymer hydrogel consisting of the soft network micro-area and the hard network framework. According to the invention, the hydrophilcity and biocompatibility of the hydrogel are improved, and the hydrophilcity has high mechanical strength, and sensitivities of rapid PH, temperature and electric field. The preparation method is simple and easy for industrialization.

Description

A kind of dual network polyalcohol hydrogel and preparation method thereof
Technical field
The present invention relates to a kind of biomedical material, especially a kind of dual network polyalcohol hydrogel and preparation method thereof with pH, temperature, electric field-sensitive.
Background technology
Hydrogel be a kind of can swelling in water or biological fluid and keep large quantity of moisture and undissolvable cross-linked polymer polymer network.Since the seventies; Because of advantages such as its unique suction and excellent biological compatibility receive Materials science and biomedical worker's research, be widely used in numerous areas such as physiological hygiene articles for use, medicine transmission system, contact lens, wastewater treatment, anti-electrostatic, sealing material, cold storage agent, solvent dehydration, wrapping material.Usually; We self can perception external environment (like temperature, pH, light, electricity, pressure etc.) small variation or stimulation, and can produce corresponding physical structure and chemical property variation even the family macromolecule gel that suddenlys change is called the environment sensitive progress in Intelligent Hydrogel.According to the response condition that stimulates to external world, it can be divided into again: temperature-responsive hydrogel, pH responsiveness aquagel, optical Response hydrogel, magnetic field responsiveness hydrogel, pressure-responsive property hydrogel, biomolecules responsiveness aquagel, electric field response hydrogel etc.
Generally contain ionizable acidity or basic group in the pH value sensitive aqueous gel network.Along with PH values changes, ionization can take place in these groups, causes dissociating of the interior intersegmental hydrogen bond of macromolecular chain of network, produces discontinuous swelling volume and changes.
Temperature-sensitive hydrogel is a kind of hydrogel that reversible expansion-contraction can take place with the variation of envrionment temperature.Along with swelling temperature is elevated to a certain temperature when above, has a certain proportion of hydrophilic and hydrophobic grouping in the gel structure, along with the hydrophobic interaction and the macromole interchain hydrogen bond action of variation of temperature group makes gel produce volume phase transition.Show as the variation of the hard opaque state from the soft vitreous state of swollen to deswelling on the macroscopic view, the variation of swelling ratio often can reach several times to tens times.
The electric field-sensitive hydrogel is meant the gel of the volume transformation that takes place along with the variation of applying direct current electric field.The electricity sensitive aquagel generally contains ionogen, and its swelling is subject to electric field (or electric current) influence.In this gellike, the counter ion of charged group move in electric field, and the variation of ionic concn causes the variation of osmotic pressure inside and outside the gel network, causes gel volume or alteration of form.
Since the eighties in 20th century, people have carried out extensive studies to the mechanical strength of gel gradually.Gong builds the notion that the equality people has proposed dual network (DN) hydrogel at first; It is that two kinds of separate hydrophilic polymer cross-linked networks are combined, and a kind of network is hard and crisp polyelectrolyte, and another kind of network is soft and tough polymkeric substance; When highly cross-linked the and second kind of network of first kind of network is lightly crosslinked; Can make local stress effectively lax through the configuration distortion of loose cross-linked network and the slip of molecular chain physical entanglement point, absorb the crackle energy, prevent that crackle from continuing to increase; Thereby improve the physical strength of gel, make gel crisp firmly and not, tough and not soft.
Many researchers has been carried out more research to polymer gels such as N-NSC 11448, acrylic amide, polyoxyethylene glycol.People such as Huang Yuewen [Huang Yuewen etc. be embedded in the sustained release research of the Frosst) in temperature and the pH value sensitive aquagel.Polymer material science and engineering, 1998,14 (6): 144-147] synthesized P (NIPAM-co-AA) hydrogel that has temperature and pH value susceptibility concurrently, and in this hydrogel embedding resistive connection bowelcancer medicine Frosst).In the medium of pH=7.4, fast during 25 ℃ of the release to birth ratio of Frosst) in aquagel membrane in the time of 37 ℃, and in 37 ℃, the medium of pH=7.4, the release to birth ratio pH=1.0's of Frosst) is much fast.People such as Tae [Tae; Et al.Temperature modulated protein release from PH/temperature-sensitive hydrogels.Biomaterials [J], 1999,20:517-521] with different acrylic amide (NIPAM) and N; N-dimethylaminopropyl USAF RH-1 is a monomer copolymerization; The hydrogel that forms is 7.4 times in the pH value, and temperature undergoes phase transition when being 37 ℃, Regular Insulin release generation considerable change therein.[Gong Jianping.Double-Network hydrogel with extremely high mechanical strength.Adv.Mater. such as Gong Jianping; 2003; 15 (14): 1155-1158] utilization gathers 2-acrylic amide-2-methyl propane sulfonic acid (PAMPS) as hard network; SEPIGEL 305 (PAAM) is as soft network, synthetic dual network (Double Net) hydrogel, and its compressive strength maximum can reach 17.2MPa.Sun Chengdong [Sun Chengdong. the preparation of phenylethylene/maleic anhydride copolymer intelligent aqueous gel capable and performance; The functional polymer journal; 2008; 3 (21): 270-274] utilize the reaction activity of maleic anhydride polyoxyethylene glycol monoesters or maleic anhydride polyoxyethylene glycol dibasic acid esters, with other active monomer-grafted or block reactions as the linking agent of other reactive polymeric thing chains, prepare gel.Generally speaking, it is lower to gather 2-acrylic amide-2-methyl propane sulfonic acid (AMPS) electroresponse gel-strength, in operating process, is easy to fragmentation; The different acrylic amide of N-(PNIPAAM), the higher and stable performance of acrylic amide (AAm) gel-strength have certain swelling behavior and gel-strength, simultaneously temperature or electric field are had responsiveness, but the speed of response can't satisfy practical requirement.The research of the dual network polyalcohol hydrogel that at present, hydrophilic monomer in-situ polymerizations such as polyoxyethylene glycol maleic anhydride ester and N-NSC 11448, acrylic amide is formed does not appear in the newspapers.
Summary of the invention
The object of the invention aims to provide dual network polyalcohol hydrogel of a kind of pH of having, temperature, electric field-sensitive and preparation method thereof.
The component of said dual network polyalcohol hydrogel is:
The multipolymer 60%～90% of polyoxyethylene glycol maleic diester and N-NSC 11448 or acrylic amide;
The homopolymer 10%～40% of N-NSC 11448 or acrylic amide.
Said dual network polyalcohol hydrogel has the susceptibility of pH, temperature, electric field.
The preparation method of said dual network polyalcohol hydrogel is following:
1) be that 200～2000 polyoxyethylene glycol (PEG), 1.86～3.96g maleic anhydride and 5～20mL organic solvent join in the reaction vessel with dried 2～20g molecular weight, sealing vacuumizes; After logical argon gas (Ar) protection, behind 65～75 ℃ of stirring 10～24h, stopped reaction; Revolve steaming; Organic solvent evaporate to dryness with in the reaction vessel obtains the polyoxyethylene glycol maleic diester, and its reaction scheme is following:
Figure BDA0000054959470000031
2) the polyoxyethylene glycol maleic diester is dissolved in 10～20mL methylene dichloride, in 100～200mL normal hexane or anhydrous diethyl ether, precipitates again, obtain intermediate product A behind the suction filtration;
3) 0.24～2.0g intermediate product A is added in 3～4mL redistilled water with 0.067～0.114g water soluble starter, 0.0616～0.132g linking agent and 0.083～0.42g N-NSC 11448 or acrylic amide; Mixing and stirring, in reaction vessel, be warming up to 75～85 ℃ of reactions behind 2～4h the dual network polyalcohol hydrogel; Or
0.083～0.28gN-NSC 11448 or acrylamide monomer after 0.24～2.0g product A and dry the purification are mixed; Add 0.026～0.064g light trigger; Add in 3～4mL redistilled water, mixing and stirring moves in the mould; Radiation 20～60min under 500～1500W UV-light promptly obtains the dual network polyalcohol hydrogel.
The reaction scheme of this reaction process and the dual network polyalcohol hydrogel that obtains at last is following:
Figure BDA0000054959470000032
In this dual network polyalcohol hydrogel, have two kinds of components: a kind of component is the multipolymer of polyoxyethylene glycol (PEG) maleic diester and N-NSC 11448 or the multipolymer of polyoxyethylene glycol (PEG) maleic diester and acrylic amide; Another component is the homopolymer of N-NSC 11448 or acrylic amide.
The structural formula of the multipolymer of the multipolymer of said polyoxyethylene glycol (PEG) maleic diester and N-NSC 11448 or polyoxyethylene glycol (PEG) maleic diester and acrylic amide (multipolymer of Ma-PEG-Ma and PNIPAM, or the multipolymer of Ma-PEG-Ma and PAAM) is following:
Figure BDA0000054959470000041
Wherein, R=-H or-CH 3
The structural formula of the homopolymer of said N-NSC 11448 or acrylic amide (PNIPAM or PAAM homopolymer) is following:
Figure BDA0000054959470000042
Wherein, R=-H or-CH 3
In step 1), said organic solvent can be selected from least a in acetone, toluene, the ETHYLE ACETATE etc.
In step 3), said water soluble starter can be selected from least a in Potassium Persulphate or the ammonium persulphate etc.; Said linking agent can be selected from least a in N,N methylene bis acrylamide (BIS), TGM 1 (EGDMA), the dimethacrylate glycol ether ester (DEGDMA) etc.; Said light trigger can be selected from 2,2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), 2,2 '-dihydroxyl-4,4 '-at least a in the dimethoxy-benzophenone etc.
For prepared dual network polyalcohol hydrogel is tested, can the dual network polyalcohol hydrogel be cut into the fritter of 5mm * 5mm * 3mm, be placed on and soak 1 day, washing in the zero(ppm) water, with the absolute ethyl alcohol dehydration, circulate twice again; It is subsequent use to place 50 ℃ of baking ovens to be dried to constant weight the product after the dehydration.
The present invention at first utilizes polyoxyethylene glycol PEG and maleic anhydride esterification reaction; Obtain the polyoxyethylene glycol that end group is a carboxyl (PEG) maleic diester; Again with itself and functional monomer in-situ polymerizations such as N-NSC 11448 or acrylic amide; Behind chemically crosslinked or UV photo-initiated crosslinking, promptly obtain dual network (DN) polyalcohol hydrogel.This kind double-network hydrogel comprises two kinds of components: a component is the multipolymer of polyoxyethylene glycol (PEG) maleic diester and N-NSC 11448 or acrylic amide, and this multipolymer forms lightly crosslinked soft network microcell; An other component is the homopolymer of N-NSC 11448 or acrylic amide, and this homopolymer forms highly cross-linked hard network skeleton.When receiving external force, lightly crosslinked network can make local stress effectively lax through the configuration distortion of loose cross-linked network and the slip of molecular chain physical entanglement point, absorbs the crackle energy, prevents that crackle from continuing to increase, thereby improves the mechanical strength of gel.Easy on the more traditional dual network polyalcohol hydrogel preparation method of this kind gel, cost is lower, and toughness increases substantially; And under different pH, temperature condition; Corresponding variation can take place in the swelling capacity of gel, and under the external dc power supply condition, gel can deflect.
The dual network polyalcohol hydrogel with pH, temperature, electric field-sensitive that the present invention is prepared has the following advantages:
1) adopt maleic anhydride polyoxyethylene glycol dibasic acid esters and aqueous functional property monomer in-situ copolymerizations such as acrylic amide or N-NSC 11448 to close the synthetic DN gel of method; Their multipolymer forms soft network microcell; And the homopolymer of functional monomer forms hard network skeleton, thereby microcell disperses external force, prevents that the effect of crack growth from realizing toughness reinforcing through effectively lax reaching when receiving external force.
2) contain groups such as more carboxyl, carboxamido-group in the gelling system, wetting ability improves, and biocompatibility improves.
3) this dual network gel mechanical property is higher, has pH, temperature, electric field-sensitive performance.
4) this kind gel will have wide practical use at biomedical sectors such as artificial cartilage, artificial haptic system, chemical valve, drug release materials.
Description of drawings
Fig. 1 is dual network polyalcohol hydrogel model configuration figure.In Fig. 1, PNIPAM is an isopropyl acrylamide polyalcohol, and PAAM is the propionic acid amide polymkeric substance.Ma-PEG-Ma is the polyoxyethylene glycol maleic diester.The multipolymer of polyoxyethylene glycol maleic diester and NSC 11448 or polyoxyethylene glycol maleic diester and propionic acid amide forms soft network, and the homopolymer of NSC 11448 or propionic acid amide forms hard frame.
Fig. 2 is the infrared spectrogram of polyoxyethylene glycol maleic diester.In Fig. 2, X-coordinate is wave number (cm -1), at 3438cm -1About tangible absorption peak is arranged, it is the hydroxyl absorption peak after the maleic anhydride open loop, at 2878cm -1Absorption peak be the C-H absorption peak of methylene radical, at 1731cm -1Absorption peak be the C=O absorption peak, 1475cm -1And 1341cm -1Absorption peak be the C-H absorption peak of two keys, 1116cm -1Be the C-O absorption peak of carboxyl, 1638cm -1Absorption peak be the flexible absorption peak of O=C-O; The 524cm in the fingerprint region -1Be the vibration peak of O=C-O, 948cm -1, 848cm -1Vibration peak for methylene radical.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of polyoxyethylene glycol maleic diester.In Fig. 3, X-coordinate is chemical shift chemicalshift (ppm), and 3.9 places are methylene radical characteristic peaks of polyoxyethylene glycol, and 4.2 places are behind polyoxyethylene glycol and the maleic anhydride esterification-OCH 2-characteristic peak.
Fig. 4 is the electric field sensitive test result of dual network polyalcohol hydrogel.In Fig. 4; X-coordinate is a compression elongation (%); Ordinate zou is compressive strength (MPa), and curve 1,2,3,4,5 is respectively the variation relation of the suffered pressure intensity of dual network polyalcohol hydrogel embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 with the compression elongation.
Fig. 5 is the compression performance test result of dual network polyalcohol hydrogel.In Fig. 5; X-coordinate is the pH value; Ordinate zou is swelling capacity (%); Wherein ■ is the variation relation of the swelling capacity of dual network polyalcohol hydrogel embodiment 1 with pH; ● be the variation relation of the swelling capacity of dual network polyalcohol hydrogel embodiment 2 with pH; ▲ be the variation relation of the swelling capacity of dual network polyalcohol hydrogel embodiment 3 with pH,
Figure BDA0000054959470000061
is the variation relation of the swelling capacity of dual network polyalcohol hydrogel embodiment 4 with pH, ◆ be the variation relation of the swelling capacity of dual network polyalcohol hydrogel embodiment 5 with pH.
Fig. 6 is the responsive test result of the pH of dual network polyalcohol hydrogel.In Fig. 6; X-coordinate be temperature (℃); Ordinate zou is swelling capacity (%); Wherein ■ is that the swelling capacity of dual network polyalcohol hydrogel embodiment 1 concerns with variation of temperature; ● the swelling capacity that is dual network polyalcohol hydrogel embodiment 2 concerns with variation of temperature; ▲ be that the swelling capacity of dual network polyalcohol hydrogel embodiment 3 concerns that with variation of temperature
Figure BDA0000054959470000062
is that the swelling capacity of dual network polyalcohol hydrogel embodiment 4 concerns with variation of temperature, ◆ the swelling capacity that is dual network polyalcohol hydrogel embodiment 5 concerns with variation of temperature.
Fig. 7 is the temperature sensitive test result of dual network polyalcohol hydrogel.In Fig. 7; X-coordinate is time (min); Ordinate zou be bending angle (°); Wherein ■ is that the bending angle of dual network polyalcohol hydrogel embodiment 1 concerns over time; ● the bending angle that is dual network polyalcohol hydrogel embodiment 2 concerns over time; ▲ be that the bending angle of dual network polyalcohol hydrogel embodiment 3 concerns over time;
Figure BDA0000054959470000063
is that the bending angle of dual network polyalcohol hydrogel embodiment 4 concerns over time,
Figure BDA0000054959470000064
be that the bending angle of dual network polyalcohol hydrogel embodiment 5 concerns over time.
Embodiment
Through embodiment the present invention is described further below.
Embodiment 1
Step 1, be 200 polyoxyethylene glycol (PEG) with the drying back 2g molecular weight that dewaters, the 1.86g maleic anhydride, the toluene of 5mL joins in the reaction vessel; Sealing vacuumizes, behind the logical nitrogen replacement; Behind 65 ℃ of stirring 10h, stopped reaction revolves steaming; Toluene evaporate to dryness with in the reaction vessel obtains the polyoxyethylene glycol maleic diester.
Step 2, the polyoxyethylene glycol maleic diester is dissolved in the methylene dichloride of 10～20mL, in 100～200mL normal hexane, precipitates again, obtain purified polyoxyethylene glycol maleic diester behind the suction filtration;
Step 3, the 0.083g N-NSC 11448 monomer after 0.24g product A and dry the purification is mixed; 0.067g Potassium Persulphate, 0.0616g N; N-methylene-bisacrylamide (BIS); Add 3～4mL redistilled water, mixing and stirring, in reaction vessel, be warming up to behind 75 ℃ of reaction 2h the DN polymer gel.
Step 4, the dual network polyalcohol hydrogel is cut into the fritter of 5mm * 5mm * 3mm then, is placed on and soaks 1 day, washing in the zero(ppm) water, with the absolute ethyl alcohol dehydration, circulate twice again; It is subsequent use to place 50 ℃ of baking ovens to be dried to constant weight in the dual network polyalcohol hydrogel sample after the dehydration.
Step 5, above-mentioned hydrogel sample is carried out compression verification on WDS-5 electronic universal test machine, its result sees Fig. 4; As can beappreciated from fig. 4, the greatest compressive strength of embodiment 1 sample is 1.02MPa.It is immersed in carries out swelling capacity test in the different PH solution, its result sees Fig. 5; As can beappreciated from fig. 5, when pH=10, the swelling capacity of gel is 5.52 * 10 to the maximum -2%.The swelling capacity test result of gel is seen Fig. 6 under condition of different temperatures; As can beappreciated from fig. 6, in the time of 15 ℃, the swelling capacity of gel is 15.6% to the maximum.In the PBS of pH=7.4 damping fluid, behind the swelling equilibrium, apply the direct supply of 15V, interelectrode distance is 5cm, observes the deflection behavior of rectangular gel and sees Fig. 7, from Fig. 7, finds out 68 ° of the maximum deflections of gel during 6min.
The chemical structure of product A is analyzed result such as Fig. 2 through the NicoletAVATAR 360FTIR IR that U.S. Nicolet company produces.From Fig. 2, can see, at 3438cm -1About tangible absorption peak is arranged, it is the hydroxyl absorption peak after the maleic anhydride open loop, at 1731cm -1Absorption peak be the C=O absorption peak, 1638cm -1Absorption peak be the flexible absorption peak of O=C-O; The 524cm in the fingerprint region -1The vibration peak that is O=C-O is the generation of further proving conclusively maleic anhydride open loop and polyoxyethylene glycol esterification reaction.
The structure of product A is analyzed through the BrukerAV400 NMR, result such as Fig. 3, and visible from Fig. 3: δ 3.9 (is the methylene radical-CH of polyoxyethylene glycol 2-characteristic peak), δ 4.3 (behind polyoxyethylene glycol and the maleic anhydride esterification-OCH 2-characteristic peak) generation that maleic anhydride open loop and polyoxyethylene glycol esterification are reacted has been described.
Embodiment 2
Step 1, be 400 polyoxyethylene glycol (PEG) with the drying back 4g molecular weight that dewaters, the 2.41g maleic anhydride, the toluene of 8mL joins in the reaction vessel; Sealing vacuumizes, behind the logical nitrogen replacement; Behind 65 ℃ of stirring 10h, stopped reaction revolves steaming; Solvent evaporate to dryness with in the reaction vessel obtains the polyoxyethylene glycol maleic diester.
Step 2, the polyoxyethylene glycol maleic diester is dissolved in the methylene dichloride of 12mL, in the 120mL anhydrous diethyl ether, precipitates again, obtain product A behind the suction filtration;
Step 3, the 0.148g acrylamide monomer after 0.45g product A and dry the purification is mixed; Add 0.026g 2,2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA) adds in the 3.5mL redistilled water; Mixing and stirring; Move in the mould, radiation 20min under the 500W UV-light promptly obtains the dual network polyalcohol hydrogel.
Step 4, the dual network polyalcohol hydrogel is cut into fritter and 10mm * 1mm * 1mm rectangular of 5mm * 5mm * 3mm then, is placed on and soaks 1 day, washing in the zero(ppm) water, with the absolute ethyl alcohol dehydration, circulate twice again; It is subsequent use to place 50 ℃ of baking ovens to be dried to constant weight in the dual network polyalcohol hydrogel sample after the dehydration.
Step 5, above-mentioned hydrogel sample is carried out compression verification on WDS-5 electronic universal test machine, its result sees Fig. 4; As can beappreciated from fig. 4, the greatest compressive strength of embodiment 1 sample is 1.12MPa.It is immersed in carries out swelling capacity test in the different PH solution, its result sees Fig. 5; As can beappreciated from fig. 5, when pH=11, the swelling capacity of gel is 5.23 * 10 to the maximum -2%.The swelling capacity test result of gel is seen Fig. 6 under condition of different temperatures; As can beappreciated from fig. 6, in the time of 15 ℃, the swelling capacity of gel is 15.9% to the maximum.In the PBS of pH=7.4 damping fluid, behind the swelling equilibrium, apply the direct supply of 15V, interelectrode distance is 5cm, observes the deflection behavior of rectangular gel and sees Fig. 7, from Fig. 7, finds out 72 ° of the maximum deflections of gel during 8min.
Embodiment 3
Step 1, be 800 polyoxyethylene glycol (PEG) with the drying back 8g molecular weight that dewaters, the 2.88g maleic anhydride, the toluene of 14mL joins in the reaction vessel; Sealing vacuumizes, behind the logical nitrogen replacement; Behind 70 ℃ of stirring 15h, stopped reaction revolves steaming; Organic solvent evaporate to dryness with in the reaction vessel obtains the polyoxyethylene glycol maleic diester.
Step 2, the polyoxyethylene glycol maleic diester is dissolved in the methylene dichloride of 16mL, in 160mL normal hexane deposition, obtains product A behind the suction filtration again.
Step 3, the 0.159g N-NSC 11448 monomer after 0.79g product A and dry the purification is mixed; 0.089g ammonium persulphate, 0.0674g TGM 1 (EGDMA); Add the 3.8mL redistilled water; Mixing and stirring, in reaction vessel, be warming up to 75 ℃ of reactions behind the 2h the DN polymer gel.
Step 4, the dual network polyalcohol hydrogel is cut into fritter and 10mm * 1mm * 1mm rectangular of 5mm * 5mm * 3mm then, is placed on and soaks 1 day, washing in the zero(ppm) water, with the absolute ethyl alcohol dehydration, circulate twice again; It is subsequent use to place 50 ℃ of baking ovens to be dried to constant weight in the dual network polyalcohol hydrogel sample after the dehydration.
Step 5, above-mentioned hydrogel sample is carried out compression verification on WDS-5 electronic universal test machine, its result sees Fig. 4; As can beappreciated from fig. 4, the greatest compressive strength of embodiment 1 sample is 1.45MPa.It is immersed in carries out swelling capacity test in the different pH solution, its result sees Fig. 5; As can beappreciated from fig. 5, when pH=10, the swelling capacity of gel is 5.43 * 10 to the maximum -2%.The swelling capacity test result of gel is seen Fig. 6 under condition of different temperatures; As can beappreciated from fig. 6, in the time of 15 ℃, the swelling capacity of gel is 15.9% to the maximum.In the PBS of pH=7.4 damping fluid, behind the swelling equilibrium, apply the direct supply of 15V, interelectrode distance is 5cm, observes the deflection behavior of rectangular gel and sees Fig. 7, from Fig. 7, finds out 63 ° of the maximum deflections of gel during 8min.
Embodiment 4
Step 1, be 1000 polyoxyethylene glycol (PEG) with the drying back 10g molecular weight that dewaters, the 3.72g maleic anhydride, the ETHYLE ACETATE of 15mL joins in the reaction vessel; Sealing vacuumizes, behind the logical nitrogen replacement; Behind 72 ℃ of stirring 20h, stopped reaction revolves steaming; With the solvent evaporate to dryness in the reaction vessel, obtain the two acid anhydrides of polyoxyethylene glycol maleic anhydride.
Step 2, the two acid anhydrides of polyoxyethylene glycol maleic anhydride are dissolved in the methylene dichloride of 18mL, in the 180mL normal hexane, precipitate again, obtain product A behind the suction filtration.
Step 3, the 0.203g acrylamide monomer after 1.25g product A and dry the purification is mixed adding 0.064g 2,2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone; Add in the 4mL redistilled water, mixing and stirring moves in the mould; Radiation 60min under the 1500W UV-light promptly obtains the dual network polyalcohol hydrogel.
Step 4, the dual network polyalcohol hydrogel is cut into fritter and 10mm * 1mm * 1mm rectangular of 5mm * 5mm * 3mm then, is placed on and soaks 1 day, washing in the zero(ppm) water, with the absolute ethyl alcohol dehydration, circulate twice again; It is subsequent use to place 50 ℃ of baking ovens to be dried to constant weight in the dual network polyalcohol hydrogel sample after the dehydration.
Step 5, above-mentioned hydrogel sample is carried out compression verification on WDS-5 electronic universal test machine, its result sees Fig. 4; As can beappreciated from fig. 4, the greatest compressive strength of embodiment 1 sample is 0.86MPa.It is immersed in carries out swelling capacity test in the different PH solution, its result sees Fig. 5; As can beappreciated from fig. 5, when pH=10, the swelling capacity of gel is 5.18 * 10 to the maximum -2%.The swelling capacity test result of gel is seen Fig. 6 under condition of different temperatures; As can beappreciated from fig. 6, in the time of 15 ℃, the swelling capacity of gel is 16.2% to the maximum.In the PBS of pH=7.4 damping fluid, behind the swelling equilibrium, apply the direct supply of 15V, interelectrode distance is 5cm, observes the deflection behavior of rectangular gel and sees Fig. 7, from Fig. 7, finds out 52 ° of the maximum deflections of gel during 7min.
Embodiment 5
Step 1, be 2000 polyoxyethylene glycol (PEG) with the drying back 20g molecular weight that dewaters, the 3.96g maleic anhydride, the acetone of 20mL joins in the reaction vessel; Sealing vacuumizes, behind the logical nitrogen replacement; Behind 75 ℃ of stirring 24h, stopped reaction revolves steaming; Solvent evaporate to dryness with in the reaction vessel obtains the polyoxyethylene glycol maleic diester.
Step 2, the polyoxyethylene glycol maleic diester is dissolved in the methylene dichloride of 20mL, in the 200mL anhydrous diethyl ether, precipitates again, obtain product A behind the suction filtration.
Step 3, the 2.8g N-NSC 11448 monomer after 0.20g product A and dry the purification is mixed; 0.114g ammonium persulphate, 0.132g triethylene glycol dimethacrylate; Add the 4mL redistilled water; Mixing and stirring, in reaction vessel, be warming up to 85 ℃ of reactions behind the 4h the DN polymer gel.
Step 4, the dual network polyalcohol hydrogel is cut into fritter and 10mm * 1mm * 1mm rectangular of 5mm * 5mm * 3mm then, is placed on and soaks 1 day, washing in the zero(ppm) water, with the absolute ethyl alcohol dehydration, circulate twice again; It is subsequent use to place 50 ℃ of baking ovens to be dried to constant weight the product after the dehydration.
Step 5, gel sample is carried out compression verification on WDS-5 electronic universal test machine, its result sees Fig. 4; As can beappreciated from fig. 4, the greatest compressive strength of embodiment 1 sample is 0.82MPa.It is immersed in carries out swelling capacity test in the different PH solution, its result sees Fig. 5; As can beappreciated from fig. 5, when pH=10, the swelling capacity of gel is 5.46 * 10 to the maximum -2%.The swelling capacity test result of gel is seen Fig. 6 under condition of different temperatures; As can beappreciated from fig. 6, in the time of 15 ℃, the swelling capacity of gel is 16.4% to the maximum.In the PBS of pH=7.4 damping fluid, behind the swelling equilibrium, apply the direct supply of 15V, interelectrode distance is 5cm, observes the deflection behavior of rectangular gel and sees Fig. 7, from Fig. 7, finds out 72 ° of the maximum deflections of gel during 8min.

Claims (2)

1. dual network polyalcohol hydrogel is characterized in that its component is:
The multipolymer 60%～90% of polyoxyethylene glycol maleic diester and N-NSC 11448 or acrylic amide;
The homopolymer 10%～40% of N-NSC 11448 or acrylic amide.
2. the preparation method of a dual network polyalcohol hydrogel is characterized in that may further comprise the steps:
1) be that 200～2000 polyoxyethylene glycol, 1.86～3.96g maleic anhydride and 5～20mL organic solvent join in the reaction vessel with dried 2～20g molecular weight, sealing vacuumizes; After the logical argon shield; Behind 65～75 ℃ of stirring 10～24h, stopped reaction revolves steaming; Organic solvent evaporate to dryness with in the reaction vessel obtains the polyoxyethylene glycol maleic diester; Said organic solvent is selected from least a in acetone, toluene, the ETHYLE ACETATE;
2) the polyoxyethylene glycol maleic diester is dissolved in 10～20mL methylene dichloride, in 100～200mL normal hexane or anhydrous diethyl ether, precipitates again, obtain intermediate product A behind the suction filtration;
3) 0.24～2.0g intermediate product A is added in 3～4mL redistilled water with 0.067～0.114g water soluble starter, 0.0616～0.132g linking agent and 0.083～0.42g N-NSC 11448 or acrylic amide; Mixing and stirring, in reaction vessel, be warming up to 75～85 ℃ of reactions behind 2～4h the dual network polyalcohol hydrogel; Or
0.083～0.28gN-NSC 11448 or acrylamide monomer after 0.24～2.0g product A and dry the purification are mixed; Add 0.026～0.064g light trigger; Add in 3～4mL redistilled water, mixing and stirring moves in the mould; Radiation 20～60min under 500～1500W UV-light promptly obtains the dual network polyalcohol hydrogel;
Said water soluble starter is selected from least a in Potassium Persulphate or the ammonium persulphate;
Said linking agent is selected from least a in N,N methylene bis acrylamide, TGM 1, the dimethacrylate glycol ether ester;
Said light trigger is selected from 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2 '-dihydroxyl-4,4 '-at least a in the dimethoxy-benzophenone.
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