CN105601950A - Sodium alginate-agar dual-network high-strength natural hydrogel material, and preparation method thereof - Google Patents
Sodium alginate-agar dual-network high-strength natural hydrogel material, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a sodium alginate-agar dual-network high-strength natural hydrogel material. The preparation method comprises following steps: a sodium alginate solution is prepared at 65 DEG C, an agar solution is prepared under 95 DEG C, and the agar solution is added into the sodium alginate solution so as to obtain a mixed solution; the mixed solution is cooled to room temperature, wherein in the cooling process, a first network is formed via hydrogen bonding crosslinking of agar molecular chains, and the mixed solution is changed into preformed hydrogel; and the preformed hydrogel is immersed into a CaCl2 aqueous solution for 4 to 6h, wherein a second network is formed via crosslinking of sodium alginate via diffusion of Ca2+ into the preformed hydrogel, and the sodium alginate-agar full physically crosslinked high-strength dual-network natural hydrogel is obtained. According to the preparation method, degradable natural plant extracts with excellent biocompatibility are taken as the raw materials to prepare the sodium alginate-agar dual-network high-strength natural hydrogel material; operation is convenient; product strength is high; and the sodium alginate-agar dual-network high-strength natural hydrogel material possesses biodegradability, and can be taken as a biological soft tissue substitute.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the high-strength natural water of a kind of sodium alginate agar dual networkThe preparation method of gel rubber material.
Background technology
Hydrogel forms water content up to 50～90% softwood as a kind of three-dimensional crosslinked network by hydrophilic high molMaterial, has similar performance to biologic soft tissue, has wide practical use in biologic soft tissue substitution material field.Particularly this soft material with high strength, high-moisture and low friction performance of double-network hydrogel, is goodCartilaginous tissue substitution material. Constantly obtain and make us aspect preparing thering is high-intensity double-network hydrogel in recent yearsThe progress of attracting attention: PEGMA/PAA double-network hydrogel (SinaNaficy, JoselitoM.Razal, PhilipG.Whitten,GordonG.Wallace,GeoffreyM.Spinks.PolymerPhysics,2012,50,423-430)、SA/PAAm double-network hydrogel (XuefengLi, ChuWu, ChengJiang, QianwenChen, DanZhou.InternationalJournalofPolymerAnalysisandCharacterization,2013,18(7):504-509)、PAMPS/PDMAAm double-network hydrogel (KatsuhisaYoshikawa, NobutoKitamura, TakayukiKurokawa,JianPingGong,YutakaNoharaandKazunoriYasuda.BMCMusculoskeletalDisorders, 2013,14 (15)), AGAR/PAAm double-network hydrogel (QiangChen, LinZhu, ChaoZhao,QiumingWang,andJieZheng.AdvanceMaterials,2013,25:4171-4176)、PVA/PAAm double-network hydrogel (JiangyuLi, ZhigangSuo, JoostJ.Vlassak.JournalofMaterialsChemistryB.2014,2:6708-6713), PDGI/PAAm double-network hydrogel (XufengLi,TakayukiKurokawa,RikuTakahashi,Md.AnamualHaque,YoufengYue,TasukuNakajima, andJianPingGong.Macromolecules, 2015,48:2277-2282) etc. These dual networksIn the preparation process of hydrogel, all adopt chemical monomer and chemical crosslinking mechanism, need to use chemical cross-linking agent, initator,The double-network hydrogel making by chemical reaction, although the artificial synthetic water gel of this class has better mechanical property,But product does not also reach requirement through abundant purifying artifact compatibility, also has one as the substitution material of soft tissueDetermine gap. Agar/Na-Alg-graft-PAAm hydrogel (RamavatarMeena, MaheshChhatbar,KamaleshPrasadandArupKSiddhanta.PolymerInternational, 2008,57:329-336), fine jadeFat/collagen composite hydrogel (Zhu Lin, He Jiankang, Liu Yaxiong, Qu Xiaoli, accounts for profit, Li Dichen, Jin Zhongmin. Xi'anUniversity of communications's journal, 2013,47 (10): 121-127), although these hydrogel main bodys adopt natural material to make materialAspect biocompatibility, optimize to some extent, but crosslinked means are single, mechanical property compared with typical double-network hydrogelCan be poor, also can not meet the requirement of the substitution material of soft tissue. Therefore research and develop one have excellent mechanical property andThe high-strength All Pure Nature hydrogel of biocompatibility has become a urgent and important job.
Above-mentioned double-network hydrogel has all used chemical monomer and chemical crosslinking, after chemical crosslinking is destroyed, cannot rebuild.
Summary of the invention
The object of the invention is, for above-mentioned present situation, to aim to provide a kind of high strength, preparation method is easy and simple to handle, consumptionTime short, repeatable strong, be applicable to large-scale production, material has the sodium alginate fine jade of good biocompatibilityThe preparation method of the high-strength natural water gel rubber material of fat dual network.
The implementation of object of the present invention is, the high-strength natural water gel rubber material of a kind of sodium alginate agar dual networkPreparation method, concrete steps are as follows:
1) sodium alginate adds in deionized water, within 30 minutes, makes it abundant dissolving 65 DEG C of stirred in water bath, obtainsSodium alginate soln; Agar is added in deionized water, 95 DEG C of stirred in water bath 30 minutes, make it fully moltenSolution, in deionized water, obtains agar solution;
The mass fraction of described sodium alginate soln is 2.85%, and the mass fraction of agar solution is 5.21～14.53%;
2) by step 1) agar solution join in sodium alginate soln, 65 DEG C of stirred in water bath 15 minutes,Obtain mixed solution;
In described mixed solution, the mass fraction of agar is 3.82～10.93%, and the mass ratio of sodium alginate and agar is1.0:(5.0～15.5)；
3) use disposable syringe to extract 5mL step 2) mixed solution, the centrifugal bubble of removing obtains transparentMixed solution uniformly;
4) by through step 3) be cooled to room temperature through the mixed solution of centrifugal de-bubble processing, in temperature-fall period, agarIt is the first heavy network that strand is cross-linked by hydrogen bond, and it is solidifying that while mixed solution forms preformed in disposable syringeGlue;
5) cut disposable syringe, from syringe tube, take out step 4) preformed gel, by solidifying preformedGlue is at 30mLCaCl2In the aqueous solution, soak Ca 4～6 hours2+Be diffused into preformed hydrogel inside and make sodium alginateBeing cross-linked is the second heavy network, obtains the full physical crosslinking high strength of sodium alginate agar dual network natural water gel;
Described CaCl2Solution molar concentration is 0.5mol/L～1.0mol/L.
It is raw material that the present invention adopts two kinds of natural plant extracts, these two kinds of natural plant extract bio-compatibleProperty is good, degradable. In preparation process, sodium alginate and agar form preformed hydrogel under the effect of hydrogen bond,Preformed hydrogel is soaked in to Ca2+In solution, Ca2+With-COO—Form physics crosslinking point and make to run through fine jadeThe sodium alginate of fat network is further cross-linked to form high crosslinked network structure, obtains the full physics of sodium alginate agar and hands overConnection high strength dual network natural water gel.
Preparation method of the present invention is easy and simple to handle, consuming time short, repeatable strong, is applicable to large-scale production; Adopt thisThe product strength of invention preparation is high, have biological degradability, belongs to environmental friendliness shaped material; There is good biologyCompatibility, has very large using value in biologic soft tissue substitution material field.
Brief description of the drawings
Fig. 1 is the molecule that sodium alginate powder and agar powder add respectively heating for dissolving formation solution in deionized waterState diagram;
Fig. 2 is the mixed molecular conformation figure of sodium alginate soln and agar solution;
Fig. 3 is the aspect graph that mixed solution forms preformed gel after cooling under hydrogen bond action;
Fig. 4 is that preformed gel is soaked in Ca2+Solution, Ca2+Be diffused into preformed hydrogel inside, make alginic acidSodium molecule chain is realized the high high strength dual network natural water gel form figure being cross-linked to form.
Detailed description of the invention
It is raw material that the present invention adopts two kinds of natural plant extracts, that agar (Agar) strand contains is abundant-OH, agar (Agar) aqueous solution is lower than below 40 DEG C, because the effect of hydrogen bond between linear molecule will formOne heavy network obtains preformed hydrogel. The applicant finds under study for action, and preformed hydrogel contains a large amount ofSodium alginate (SA) aqueous solution, sodium alginate (SA) strand is by mannuronic acid (M section) and ancient sieveUronic acid (G section) composition, in the aqueous solution in G section-COO—Meeting and Ca2+There is ion complexation,Like this on sodium alginate (SA) different molecular chain-COO—Also just form the second heavy cross-linked network by complexingNetwork obtains full physical crosslinking double-network hydrogel. This dual network structure under effect of stress, the sodium alginate of rigidity(SA) the first heavy network can first break, Ca2+With-COO—The physics crosslinking point conduct " sacrifice key " forming,By the fracture dissipation energy of " sacrifice key ", prevent the generation of macroscopic failure, simultaneously sodium alginate (SA) firstBreak many fragments of forming of heavy network become the physical crosslinking point of agar (Agar) the second heavy network, to gel netNetwork plays the effect of enhancing.
The heavy network fragment of sodium alginate (SA) first can further break, and utilizes the destruction of " sacrifice key "Dissipate the energy that gel network produces under effect of stress, reduce the destruction of stress to hydrogel, " sacrifice key " composedGive the full physical crosslinking double-network hydrogel of sodium alginate agar high strength. Ca2+On sodium alginate (SA) strand-COO—Form physics crosslinking point destroyed after, Ca in solution environmental2+Can be again and sodium alginate(SA) on strand-COO—Complexing produces new crosslinking points.
The advantage of this physical crosslinking system that the present invention adopts is can rebuild after strand crosslinked destroyed,Therefore give the mechanical property of hydrogel excellence. Sodium alginate (SA) and agar (Agar) are all from algaeThe natural plant extract that middle extraction obtains, has good histocompatbility, in biologic soft tissue substitution materialThere is huge application prospect in field.
Describe the present invention in detail below in conjunction with accompanying drawing. In figure
SA powderAgar powderAgar strandSA strand Ca2+Hydrogen bond
Concrete steps of the present invention are as follows:
1) sodium alginate (SA) powder adds in deionized water, within 30 minutes, makes it to fill 65 DEG C of stirred in water bathDivide and dissolve, obtain the aqueous solution of sodium alginate (SA) molecular conformation; Agar powder is added in deionized water,95 DEG C of stirred in water bath 30 minutes, make it to be fully dissolved in deionized water, obtain agar (Agar) molecule shapeThe aqueous solution (seeing Fig. 1) of state;
The mass fraction of described sodium alginate (SA) is 2.85%, the mass fraction of agar (Agar) is 5.21-14.53％；
2) by step 1) agar solution add in sodium alginate soln, 65 DEG C of stirred in water bath 15 minutes,Obtain the mixed solution of molecular conformation shown in Fig. 2;
The mass fraction of agar in described mixed solution (Agar) is 3.82～10.93%, sodium alginate (SA) withThe mass ratio of agar (Agar) is 1.0:(5.0～15.5);
3) use disposable syringe to extract 5mL step 2) mixed solution, the centrifugal bubble of removing obtains transparentMixed solution uniformly;
The described centrifugal bubble of removing is that disposable syringe is fixed in centrifuge tube, adds 10mL in centrifuge tubeDeionized water, the temperature of deionized water is 95 DEG C, is under 10000rpm condition centrifugal 15 minutes at rotating speed.
4) by step 3) be cooled to room temperature through the mixed solution of centrifugal de-bubble processing, in temperature-fall period, agar
(Agar) to be cross-linked by hydrogen bond be the first heavy network to strand, and mixed solution forms in disposable syringe simultaneouslyThe preformed gel of form shown in Fig. 3;
5) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at CaCl2In the aqueous solution, soak Ca 4～6 hours2+Being diffused into preformed hydrogel inside, sodium alginate (SA) is cross-linked isDouble network, obtains the natural water-setting of the full physical crosslinking high strength of sodium alginate agar dual network of form as shown in Figure 4Glue;
Described CaCl2Solution molar concentration is 0.5mol/L～1.0mol/L.
With specific embodiment in detail the present invention is described in detail below:
Embodiment 1
1) 0.88g sodium alginate (SA) powder adds in 30mL deionized water, 65 DEG C of stirred in water bath 30Minute make it abundant dissolving, obtain mass fraction and be 2.85% sodium alginate (SA) solution; By 4.4g agar (Agar)Powder adds in 80mL deionized water, 95 DEG C of stirred in water bath 30 minutes, makes it to be fully dissolved in deionizationWater, obtains mass fraction and is 5.21% agar (Agar) solution;
2) by step 1) agar (Agar) solution add in sodium alginate (SA) solution, 65 DEG C of water-bathsMiddle stirring 15 minutes, obtains mixed solution;
The mass fraction of agar in described mixed solution (Agar) is 3.82%, sodium alginate in described mixed solution(SA) be 1.0:5.0 with the mass ratio of agar (Agar);
3) use disposable syringe to extract 5mL step 2) mixed solution, the centrifugal bubble of removing obtains transparentMixed solution uniformly;
4) by step 3) be cooled to room temperature through the mixed solution of centrifugal de-bubble processing, in temperature-fall period, agar(Agar) to be cross-linked by hydrogen bond be the first heavy network to strand, and mixed solution forms in disposable syringe simultaneouslyPreformed gel;
5) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at 30mL1mol/LCaCl2In the aqueous solution, soak Ca 4 hours2+Be diffused into preformed hydrogel inside and make sodium alginate (SA)Being cross-linked is the second heavy network, obtains the full physical crosslinking high strength of sodium alginate agar dual network natural water gel.
Experiment records the full physical crosslinking high strength of the sodium alginate agar dual network natural water gel of the present embodiment gainedTensile break strength is 120KPa, and compression failure stress is 450KPa.
Embodiment 2, with embodiment 1, different,
1) 5.80g agar (Agar) powder is added in 80mL deionized water, 95 DEG C of stirred in water bath 30Minute, make it to be fully dissolved in deionized water, obtain mass fraction and be 6.76% agar (Agar) solution;
2) by step 1) agar (Agar) solution add in sodium alginate (SA) solution, 65 DEG C of water-bathsMiddle stirring 15 minutes, obtains mixed solution;
The mass fraction of agar in described mixed solution (Agar) is 4.97%, sodium alginate in described mixed solution(SA) be 1.0:6.6 with the mass ratio of agar (Agar);
5) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at 30mL0.75mol/LCaCl2In the aqueous solution, soak Ca 5 hours2+Be diffused into preformed hydrogel inside and make sodium alginate(SA) being cross-linked is the second heavy network, obtains the full physical crosslinking high strength of sodium alginate agar dual network natural water gel.
Experiment records the full physical crosslinking high strength of the sodium alginate agar dual network natural water gel of the present embodiment gainedTensile break strength is 160KPa, and compression failure stress is 500KPa.
Embodiment 3, with embodiment 1, different,
1) 8.80g agar (Agar) powder is added in 80mL deionized water, 95 DEG C of stirred in water bath 30Minute, make it to be fully dissolved in deionized water, obtain mass fraction and be 9.91% agar (Agar) solution;
2) by step 1) agar (Agar) solution add in sodium alginate (SA) solution, 65 DEG C of water-bathsMiddle stirring 15 minutes, obtains mixed solution;
The mass fraction of agar in described mixed solution (Agar) is 7.35%, sodium alginate in described mixed solution(SA) be 1.0:10.0 with the mass ratio of agar (Agar);
5) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at 30mL0.5mol/LCaCl2In the aqueous solution, soak Ca 6 hours2+Be diffused into preformed hydrogel inside and make sodium alginate (SA)Being cross-linked is the second heavy network, obtains the full physical crosslinking high strength of sodium alginate agar dual network natural water gel.
Experiment records the full physical crosslinking high strength of the sodium alginate agar dual network natural water gel of the present embodiment gainedTensile break strength is 240KPa, and compression failure stress is 530KPa.
Embodiment 4, with embodiment 1, different,
1) 13.6g agar (Agar) powder is added in 80mL deionized water, 95 DEG C of stirred in water bath 30Minute, make it to be fully dissolved in deionized water, obtain mass fraction and be 14.53% agar (Agar) solution;
2) by step 1) agar (Agar) solution add in sodium alginate (SA) solution, 65 DEG C of water-bathsMiddle stirring 15 minutes, obtains mixed solution;
The mass fraction of agar in described mixed solution (Agar) is 10.93%, sodium alginate in described mixed solution(SA) be 1.0:15.5 with the mass ratio of agar (Agar);
5) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at 30mL0.5mol/LCaCl2In the aqueous solution, soak Ca 6 hours2+Be diffused into preformed hydrogel inside and make sodium alginate (SA)Being cross-linked is the second heavy network, obtains the full physical crosslinking high strength of sodium alginate agar dual network natural water gel.
Experiment records the full physical crosslinking high strength of the sodium alginate agar dual network natural water gel of the present embodiment gainedTensile break strength is 310KPa, and compression failure stress is 600KPa.
For confirming the effect of two components, the applicant has done contrast experiment with one-component, and specific experiment is as follows:
Comparative example 1
1) 0.88g sodium alginate (SA) powder adds in 110mL deionized water, 65 DEG C of stirred in water bath 30Minute make it abundant dissolving, obtain mass fraction and be 0.79% sodium alginate (SA) solution;
2) use disposable syringe to extract 5mL step 1) sodium alginate (SA) solution, centrifugal except degassingBubble obtains transparent uniform sodium alginate (SA) solution;
3) by step 2) sodium alginate (SA) solution of the centrifugal de-bubble processing of process in disposable syringe is coldBut to room temperature, in temperature-fall period, sodium alginate (SA) solution is cross-linked shape in disposable syringe by hydrogen bondBecome preformed gel;
4) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at 30mL1mol/LCaCl2In the aqueous solution, soak Ca 4 hours2+Be diffused into preformed hydrogel inside and make sodium alginate (SA)Form high cross-linked network, obtain physical crosslinking list network natural water gel.
The tensile break strength that experiment records this comparative example gained list network natural water gel is lower than 20KPa, and compression is brokenBad stress is lower than 50KPa.
Comparative example 2
1) 13.6g agar (Agar) powder is added in 110mL deionized water, 95 DEG C of stirred in water bath 30Minute, make it to be fully dissolved in deionized water, obtain mass fraction and be 10.93% agar (Agar) solution;
2) use disposable syringe to extract 5mL step 1) agar (Agar) solution, the centrifugal bubble of removing obtainsTo transparent uniform agar (Agar) solution;
3) by step 2) agar (Agar) solution of the centrifugal de-bubble processing of process in disposable syringe is cooled toRoom temperature, in temperature-fall period, agar (Agar) solution is cross-linked and in disposable syringe, is formed gel by hydrogen bond;
4) cut disposable syringe, from syringe tube, take out preformed gel, by preformed gel at 30mL1mol/LCaCl2In the aqueous solution, soak Ca 4 hours2+Be diffused into preformed hydrogel inside and make agar (Agar)Be cross-linked to form high cross-linked network, obtain physical crosslinking list network natural water gel.
The tensile break strength that experiment records this comparative example gained list network natural water gel is 100KPa, compression failureStress is 500KPa.
The tensile break strength of the hydrogel of above-described embodiment, comparative example and compression failure stress are as following table 1:
Table 1: agar (Agar) hydrogel, sodium alginate (SA) hydrogel and sodium alginate agar hydrogelThe contrast of tensile break strength and compression failure stress sees the following form.
Can find out by the data in form:
The tensile break strength of the three kinds of full physical crosslinking high strength of sodium alginate agar dual network natural water gels all higher thanThe physical crosslinking list network natural water gel of one pack system. Comparative example 2 has identical agar (Agar) with embodiment 3Mass fraction, the full physical crosslinking of sodium alginate agar that embodiment 3 obtains by adding a small amount of sodium alginate (SA)High strength dual network natural water gel has significantly improved the compression failure stress (having improved 100KPa) of hydrogel. WhenIn the full physical crosslinking high strength of sodium alginate agar dual network natural water gel the mass fraction of agar (Agar) by3.82%, 4.97.%, 7.35%, 10.93% increase gradually and sodium alginate agar mass ratio by 1:5,1:6.6,1:10,When 1:15.5. reduces gradually, its tensile break strength and compression failure stress increase gradually, and mechanical property significantly improves.
Other unspecified part all belongs to prior art.
Claims (2)
1. a preparation method for the high-strength natural water gel rubber material of sodium alginate agar dual network, is characterized in that:Concrete steps are as follows:
1) sodium alginate adds in deionized water, within 30 minutes, makes it abundant dissolving 65 DEG C of stirred in water bath, obtainsSodium alginate soln; Agar is added in deionized water, 95 DEG C of stirred in water bath 30 minutes, make it fully moltenSolution, in deionized water, obtains agar solution;
The mass fraction of described sodium alginate soln is 2.85%, and the mass fraction of agar solution is 5.21～14.53%;
2) by step 1) agar solution join in sodium alginate soln, 65 DEG C of stirred in water bath 15 minutes,Obtain mixed solution;
In described mixed solution, the mass fraction of agar is 3.82～10.93%, and the mass ratio of sodium alginate and agar is1.0:(5.0～15.5)；
3) use disposable syringe to extract 5mL step 2) mixed solution, the centrifugal bubble of removing obtains transparentMixed solution uniformly;
4) by through step 3) be cooled to room temperature through the mixed solution of centrifugal de-bubble processing, in temperature-fall period, agarIt is the first heavy network that strand is cross-linked by hydrogen bond, and it is solidifying that while mixed solution forms preformed in disposable syringeGlue;
5) cut disposable syringe, from syringe tube, take out step 4) preformed gel, by solidifying preformedGlue is at 30mLCaCl2In the aqueous solution, soak Ca 4～6 hours2+Be diffused into preformed hydrogel inside and make sodium alginateBeing cross-linked is the second heavy network, obtains the full physical crosslinking high strength of sodium alginate agar dual network natural water gel;
Described CaCl2Solution molar concentration is 0.5mol/L～1.0mol/L.
2. the preparation of the high-strength dual network natural water of a kind of sodium alginate agar according to claim 1 gel rubber materialMethod, is characterized in that: step 3) the described centrifugal bubble of removing is that disposable syringe is fixed in centrifuge tube,In centrifuge tube, add 10mL deionized water, the temperature of deionized water is 95 DEG C, is 10000rpm bar at rotating speedUnder part centrifugal 15 minutes.
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