CN108409997A - A kind of preparation method of the superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus - Google Patents
A kind of preparation method of the superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08J2451/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
Abstract
The invention discloses a kind of preparation methods of the superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus.This method is the single cross-linked hydrogel that must be physical crosslinking with Cellulose nanocrystal to be made by host-guest interaction, and before secondary cross-linking, realized by external force and be pre-stretched orientation to single cross-linked hydrogel, and Fe is added3+Secondary cross-linking can in fixed network Cellulose nanocrystal must orientation, mechanical property more preferably anisotropy hydrogel is made.By adjusting acrylic acid and acrylamide monomer ratio, iron concentration and pre-stretching degree, the properties such as water content and the mechanical property of hydrogel are can control, the purposes range of hydrogel is expanded.Hydrogel intensity prepared by the present invention program is high, and new thinking is provided the shortcomings that conventional hydrogels poor mechanical property to make up；And double physical crosslinking methods that hydrogel is prepared in this programme are simple and practicable, of low cost, wherein fixed whisker's orientation is even more a kind of new method for preparing anisotropy hydrogel.
Description
Technical field
The present invention relates to a kind of preparation methods of the superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus, belong to
In composite material, polymer-function material field.
Background technology
Conventional hydrogels are greatly limited because haveing the shortcomings that intensity is insufficient, toughness is poor in actual application
In the application of the numerous areas such as agricultural, biological medicine, organizational project.The feasible network structure of reasonable design is then to improve water-setting
One big key point of glue mechanical property, introduces effective energy dissipation mechanism, makes hydrogel still energy when occurring compared with large deformation
The integrality of its cross-linked network is maintained to a certain extent.The many different water gels of researcher's design construction at present
System, more representational high intensity hydrogel include topological hydrogel, double-network hydrogel, Nanometer composite hydrogel etc..
(Yasushi Okumura,Kohzo Ito,Advanced Materials,2001,13,485-487.Gong J.P.,
Katsuyama Y.；Kurokawa T.,Advanced Materials,2003,15,1155-1158.Haraguchi K.,
Takehisa T., Advanced Materials, 2002,14,1120-1124.) wherein, the three-dimensional of Nanometer composite hydrogel is handed over
Networking network is combined by the substrate polymer strand of " soft " of Nano filling and polymerization generation compared with " hard " and is formed, and can specifically be passed through
It physically or chemically interacts or two kinds of crosslinking methods and the mode deposited is completed to be crosslinked.And in recent years to renewable resource
The extensive concern of cellulosic material, application of the Cellulose nanocrystal body in compound hydrogel material also gradually increase.It is reported that
The addition of Cellulose nanocrystal body with hydrophilic surface can effectively improve the mechanical strength of Nanometer composite hydrogel, certain
Under the conditions of be additionally favorable for the preparation of such as syringeability, self-healing functionalization hydrogel.(Yang J.,Zhao J.J.,Han
C.R.,Cellulose,2014,21,541-551.Rui M.A.Domingues,Marta Silva,Pavel
Gershovich,Bioconjugate Chem.,2015,26,1571-1581.Jason R.McKee,Eric A.Appel,
Jani Seitsonen, Advanced Functional Materials, 2014,24,2706-2713.) while thering is research to send out
Existing, the Physical interactions such as electrostatic interaction, hydrophobic effect, ion coordination effect are considered as reproducible " sacrificing key ", can replace
Irreversible covalent bond in conventional hydrogels network, to enhance its fatigue resistance and self-healing.(Tao Lin Sun,
Takayuki Kurokawa,Shinya Kuroda,Nature Materials,2013,12,932-937.Zhang T.,
Cheng Q.,Ye D.,Carbohydrate Polymers,2017,169,139-148.Peng Lin,Shuanhong Ma,
Xiaolong Wang,Advanced Materials,2015,27,2054-2059.)
The method of the present invention must be Nano filling with the Cellulose nanocrystal with high-modulus, high length-diameter ratio, in Conventional nano
The effect for improving mechanical strength is not only played in composite hydrogel network, moreover it is possible to as polyfunctional crosslinking agent, be conducive to Nano filling
Interface compatibility between matrix.In addition, being opened by soft tissues such as cartilage, the muscle of ordered structure such as excellent in mechanical performance
Hair, attempting the fixed Cellulose nanocrystal in the converging network of pre-stretching in of the invention must be orientated, and thus prepare mechanical property
The high-sequential Nanometer composite hydrogel of superelevation.
Invention content
The technical problem to be solved in the present invention is to provide a kind of superhigh intensity anisotropy containing Cellulose nanocrystal palpus
The preparation method of hydrogel.
The preparation method of the present invention includes the following steps：
A kind of preparation method of the superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus, including walk as follows
Suddenly：
1) by guest compound, the host compound containing Cellulose nanocrystal palpus, monomeric acrylamide (AM), monomer third
Olefin(e) acid (AA), initiator, accelerator mixing, and cause polymerization, single cross-linked hydrogel based on host-guest interaction is made；
2) apply axial force to gained list cross-linked hydrogel to be pre-stretched it, cause the cellulose in cross-linked network
Nano whisker is along draw direction ordered arrangement；
3) single cross-linked hydrogel of different pre-stretching ratios is immersed in iron content deionized water solution, after reaching swelling equilibrium, then
It is impregnated in distilled water to remove the iron ion having more than needed in cross-linked network, there are final be made double physics of superpower mechanical property to hand over
Join hydrogel.
Preferably, the host compound is the Cellulose nanocrystal palpus (CD-CNCs) of grafted by beta cyclodextrin, the object
Compound is acrylamide graft adamantane (Ad-AM).
Preferably, the host compound CD-CNCs is prepared by single step reaction：The cellulose that sulphuric acid hydrolysis is obtained
After nano whisker is dispersed in distilled water, instills cyclodextrin alkaline solution and be uniformly mixed, add epoxychloropropane (EPI)
The mechanical agitation at 40 DEG C is dried in vacuo after purified processing to get to host compound white pigmented samples after reaction.
Preferably, the molar ratio of the epoxychloropropane and cyclodextrin of addition is 10：1.
Preferably, under certain condition, beta-cyclodextrin and reacting ethylenediamine obtain grafted by beta cyclodextrin ethylenediamine, and fiber
Plain nano whisker generates carboxyl after TEMPO (tetramethyl piperidine nitrogen oxides) oxidation processes, by grafted by beta cyclodextrin ethylenediamine
It must react to form amido bond under certain condition with the Cellulose nanocrystal with carboxyl, products therefrom equally can be used as main body chemical combination
Object.Wherein, ethylenediamine can also such as hexamethylene diamine replacement of other compounds.
Preferably, the cellulose origin includes ascidian cellulose, alginate fibre element, cotton linters cellulose, wood pulp cellulose
Element.
Preferably, the guest compound Ad-AM is prepared with the following method：By adamantanamine hydrochloride and triethylamine
It is dissolved in tetrahydrofuran solution, ice bath stirring 2 hours after acryloyl chloride is added, then be continuously stirred at room temperature 12 hours, it is final to locate
Reason obtains guest compound.
Triethylamine can promote reaction to carry out as attached sour agent, and acryloyl chloride is slightly excessive to be also conducive to improve adamantanamine hydrochloride
Equilibrium conversion.
Preferably, initiator described in step 1) is potassium peroxydisulfate (KPS), the accelerator is tetramethylethylenediamine
(TEMED), using adding thermal-initiated polymerization.
Preferably, the molar ratio of acrylic acid and acrylamide is (0.2~0.3) in step 1)：1.
Preferably, it is 400%~900% to the pre-stretching degree that single cross-linked hydrogel applies in step 2).
Preferably, in step 3) iron ion aqueous solution iron ion a concentration of 0.01~0.3mol/L.
A kind of superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus, adopts and is prepared into the aforedescribed process
It arrives.
The formation of single cross-linked hydrogel relies primarily on the β-CD energy and guest compound of Cellulose nanocrystal palpus surface modification
In include adamantane structure combined by host-guest interaction, loose network structure contributes to the elasticity of material, fracture
Elongation reaches as high as about 1700%, and the excellent elasticity of single cross-linked hydrogel carries out it after being on the basis of pre-stretching orientation；
It is subsequently introduced iron ion, electrostatic interaction is generated with electronegative carboxyl on acrylamide and acrylic acid copolymer segment, relies on
Electrostatic attraction realizes that the fixation to hydrogel cross-linked network, that is, the cellulose for completing in the stretching direction to arrange high-sequential are received
The fixation of meter Jing Xu, double physical cross-linking hydrogels of final obtained high strength.
Prestretching during the double cross-linked hydrogels of preparation can give full play to the Cellulose nanocrystal palpus as filler
The advantage of high length-diameter ratio, high intensity hydrogel obtained are in anisotropy, in the case where elongation at break is 105%, are drawn
Intensity is stretched up to 53.6MPa, toughness 41.9MJ/m3。
By changing acrylic acid and acrylamide monomer ratio and iron concentration, double physical cross-linking hydrogel nets are influenced
The crosslink density of network structure；And change the pre-stretching degree of single cross-linked hydrogel under outer force effect, have in cross-linked network higher
The Cellulose nanocrystal palpus of draw ratio can be arranged as more orderly structure with the increase of pre-stretching degree.Finally, it is based on master
Object interacts and electrostatic interaction, obtains that a series of properties such as water content and mechanical property are different to be received containing cellulose
The superhigh intensity hydrogel of meter Jing Xu.
Superhigh intensity anisotropy hydrogel mechanical property containing Cellulose nanocrystal palpus prepared by the method for the present invention is excellent
It is different, and preparation process is simple and easy to operate, compare with the existing technology, the present invention has innovation as follows：
The present invention is using acrylamide and acrylic acid copolymer as substrate, and Cellulose nanocrystal must be Nano filling, pass through master
Object-electrostatic interaction completes double physical crosslinkings and forms the composite hydrogel with superelevation mechanical property, and in the preparation
By single cross connection-external force pre-stretching-, cross-linking process simply and efficiently prepares anisotropy hydrogel again, and mechanical property is further
It is promoted.The reason crosslinking of first weight is based on host-guest interaction, its main feature is that crosslink density is relatively low, the contribution of loose cross-linked network
In the elasticity of single cross-linked hydrogel, pre-stretching orientation provides basis for after；Second be physical crosslinking again then depend on ferric iron from
Electrostatic interaction between son and one or more carboxylate radical anions, its main feature is that hydrogel crosslink density can be effectively improved,
It is obviously improved mechanical property.Under external force, physical crosslinking close and reversible in network structure point while or lost energy
The effective way of amount, and the process that Cellulose nanocrystal palpus filler is extracted from matrix equally contributes energy dissipation,
It can achieve the effect that activeness and quietness.
In summary, height is had based on single cross-linked hydrogel that host-guest interaction between cyclodextrin and adamantane is built
Elasticity can occur to be to complete to stretch the network base being orientated without rupturing compared with large deformation in the case where axial force stretches
Plinth；And the secondary cross-linking based on iron ion Yu carboxyl electrostatic attraction, hydrogel crosslink density is greatly improved, can effectively fix drawing
Hydrogel after stretching keeps the high-sequential arrangement architecture for the Cellulose nanocrystal palpus realized by force-extension.It stretches in this way
Hydrogel from can be changed into anisotropy to the same sex, has been given full play to Cellulose nanocrystal and must be used as and filled out by the preparation method of orientation
The characteristics of expecting high length-diameter ratio, it is final that the anisotropy hydrogel with superhigh intensity is made.
Whisker's orientation is fixed after proposing external force pre-stretching simultaneously in the present invention, to prepare the side of anisotropy hydrogel
Method, it is simpler easy, of low cost and applied widely compared to prior art means；It must itself in conjunction with Cellulose nanocrystal
The characteristics of high-modulus, high length-diameter ratio, the method for the present invention are a kind of new approaches for the high-efficient simple for preparing anisotropy hydrogel.
Description of the drawings
Fig. 1 is the pictorial diagram of present invention gained hydrogel at room temperature, and wherein a is that single cross connection obtained is fine in comparative example 1
The pictorial diagram of hydrogel is tieed up, b is the pictorial diagram of the double cross-linked hydrogels of 4 gained of embodiment；
Fig. 2 is the present invention double physical crosslinking cellulose aquagels obtained in different acrylic acid and acrylamide molar ratio
Stress-strain curve diagram, each curve indicates the preparation condition based on embodiment 3 and 4 respectively in figure, adjusts acrylic acid and propylene
The stress-strain relation of the double physical crosslinking cellulose aquagels of gained when the molar ratio of amide is 0.1,0.2,0.3,0.5；
Fig. 3 be the embodiment of the present invention 4 to 7 under the conditions of different pre-stretching ratios double physical crosslinking celluloses obtained respectively to
The stress-strain curve diagram of anisotropic hydrogel；
Fig. 4 is the atomic force microscopy that the embodiment of the present invention 6 prepares gained anisotropy hydrogel, it is observed that
Orientation texture of the hydrogel surface along force-extension direction.
Specific implementation mode
The content that following embodiment further illustrates the present invention, but should not be construed limitation of the present invention.It is not carrying on the back
In the case of from spirit of that invention and essence, to modifications or substitutions made by the method for the present invention, step or condition, this is belonged to
The range of invention.If non-special declaration, technological means used in embodiment is the conventional means known to those skilled in the art.
Embodiment 1
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.42g acrylic acid and 2.58g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.2), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, keeps former long, at room temperature in the FeCl of 0.01mol/L3It is impregnated 48 hours in solution；After taking-up
It is placed in distilled water to impregnate 48 hours and reaches swelling equilibrium.After tested, the elasticity modulus of gained secondary cross-linking hydrogel is
2.75MPa, toughness 6.51MJ/m3。
Embodiment 2
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.42g acrylic acid and 2.58g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.2), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, keeps former long, at room temperature in the FeCl of 0.3mol/L3It is impregnated 48 hours in solution；After taking-up
It is placed in distilled water to impregnate 48 hours and reaches swelling equilibrium.After tested, the elasticity modulus of gained secondary cross-linking hydrogel is
8.13MPa, toughness 12.51MJ/m3。
Embodiment 3
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.23g acrylic acid and 2.27g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.1), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, keeps former long, at room temperature in the FeCl of 0.1mol/L3It is impregnated 48 hours in solution；After taking-up
It is placed in distilled water to impregnate 48 hours and reaches swelling equilibrium.After tested, the elasticity modulus of gained secondary cross-linking hydrogel is
0.45MPa, toughness 4.43MJ/m3。
Embodiment 4
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.58g acrylic acid and 2.42g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.3), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, keeps former long, at room temperature in the FeCl of 0.1mol/L3It is impregnated 48 hours in solution；After taking-up
It is placed in distilled water to impregnate 48 hours and reaches swelling equilibrium.After tested, the elasticity modulus of gained secondary cross-linking hydrogel is
25.72MPa, toughness 18.56MJ/m3。
Embodiment 5
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.58g acrylic acid and 2.42g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.3), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, force-extension to 5 times long i.e. elongation strain of original is 400%, is fixed with adhesive tape, is existed at room temperature
The FeCl of 0.1mol/L3It is impregnated 48 hours in solution；Taking-up, which is placed in distilled water to impregnate 48 hours, reaches swelling equilibrium.Through surveying
The elasticity modulus of examination, gained secondary cross-linking hydrogel is 103.42MPa, toughness 25.24MJ/m3。
Embodiment 6
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.58g acrylic acid and 2.42g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.3), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, force-extension to 10 times long i.e. elongation strain of original is 900%, is fixed with adhesive tape, at room temperature
In the FeCl of 0.1mol/L3It is impregnated 48 hours in solution；Taking-up, which is placed in distilled water to impregnate 48 hours, reaches swelling equilibrium.Through surveying
The elasticity modulus of examination, gained secondary cross-linking hydrogel is 133.01MPa, toughness 41.92MJ/m3。
Embodiment 7
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.58g acrylic acid and 2.42g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.3), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).Hydrogel is taken out after the completion of polymerization to cut
It is cut into the cuboid of appropriate length and width, force-extension to 15 times long i.e. elongation strain of original is 1400%, is fixed with adhesive tape, at room temperature
In the FeCl of 0.1mol/L3It is impregnated 48 hours in solution；Taking-up, which is placed in distilled water to impregnate 48 hours, reaches swelling equilibrium.To institute
It obtains gel and carries out stress-strain test.
Comparative example 1
The grafted by beta cyclodextrin Cellulose nanocrystal palpus aqueous dispersions 7.5g for taking a concentration of 1.05wt%, is added with stirring and contains
0.5g acrylamide graft adamantane, stabilization add 0.42g acrylic acid and 2.58g acrylamide (i.e. acrylic acid after twenty minutes
Molar ratio with acrylamide is 0.3), to be stirred 2 hours under 55 DEG C of heating water baths.Stop heating after mixing, 5mg is added
Initiator potassium persulfate and 2.5mg accelerator tetramethylethylenediamines continue stirring and are transferred in glass mold after five minutes, 60
It is reacted 12 hours in the environment of DEG C, thermal-initiated polymerization generates single cross-linked hydrogel (m-Gel).After tested, gained single cross joins water-setting
The elasticity modulus of glue is 0.01MPa, and elongation at break 1800% shows very high elongation at break and low elastic modulus,
There is high resiliency.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of preparation method of the superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus, which is characterized in that packet
Include following steps：
1) by guest compound, the host compound containing Cellulose nanocrystal palpus, monomeric acrylamide (AM), monomeric acrylic
(AA), initiator, accelerator mixing, and cause polymerization, single cross-linked hydrogel based on host-guest interaction is made；
2) apply axial force to gained list cross-linked hydrogel to be pre-stretched it, cause the cellulose nanometer in cross-linked network
Whisker is along draw direction ordered arrangement；
3) single cross-linked hydrogel of different pre-stretching ratios is immersed in iron content deionized water solution, after reaching swelling equilibrium, then is being steamed
It is impregnated in distilled water to remove the iron ion having more than needed in cross-linked network, it is final that double physical crosslinking water with superpower mechanical property are made
Gel.
2. preparation method according to claim 1, which is characterized in that the host compound is the fibre of grafted by beta cyclodextrin
The plain nano whisker (CD-CNCs) of dimension, the guest compound are acrylamide graft adamantane (Ad-AM).
3. preparation method according to claim 2, which is characterized in that the host compound CD-CNCs passes through a step
It is prepared by reaction：After the Cellulose nanocrystal that sulphuric acid hydrolysis obtains must be dispersed in distilled water, it is molten to instill cyclodextrin alkalinity
Liquid is uniformly mixed, and adds epoxychloropropane (EPI) mechanical agitation at 40 DEG C, and vacuum is dry after purified processing after reaction
It is dry to get to host compound white pigmented samples.
4. preparation method according to claim 2, which is characterized in that the guest compound Ad-AM uses such as lower section
It is prepared by method：Adamantanamine hydrochloride and triethylamine are dissolved in tetrahydrofuran solution, ice bath stirring 2 hours after acryloyl chloride are added,
It is continuously stirred at room temperature again 12 hours, final process obtains guest compound.
5. preparation method according to claim 3, which is characterized in that the epoxychloropropane of addition and the molar ratio of cyclodextrin
It is 10:1.
6. preparation method according to claim 1, which is characterized in that initiator described in step 1) is potassium peroxydisulfate
(KPS), the accelerator is tetramethylethylenediamine (TEMED), using adding thermal-initiated polymerization.
7. preparation method according to claim 1, which is characterized in that the molar ratio of acrylic acid and acrylamide in step 1)
For (0.2~0.3)：1.
8. preparation method according to claim 1, which is characterized in that the prestretching applied to single cross-linked hydrogel in step 2)
The degree of stretching is be stretched to former length 5 times~10 times.
9. preparation method according to claim 1, which is characterized in that the concentration of iron ion in step 3) iron ion aqueous solution
For 0.01~0.3mol/L.
10. a kind of superhigh intensity anisotropy hydrogel containing Cellulose nanocrystal palpus, which is characterized in that use claim
1~9 any one of them method is prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810270159.3A CN108409997B (en) | 2018-03-29 | 2018-03-29 | Preparation method of ultrahigh-strength anisotropic hydrogel containing cellulose nanowhiskers |
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| CN201810270159.3A CN108409997B (en) | 2018-03-29 | 2018-03-29 | Preparation method of ultrahigh-strength anisotropic hydrogel containing cellulose nanowhiskers |
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