WO2019095751A1 - 一种纤维素/二维层状材料复合水凝胶及其制备方法 - Google Patents

一种纤维素/二维层状材料复合水凝胶及其制备方法 Download PDF

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WO2019095751A1
WO2019095751A1 PCT/CN2018/100240 CN2018100240W WO2019095751A1 WO 2019095751 A1 WO2019095751 A1 WO 2019095751A1 CN 2018100240 W CN2018100240 W CN 2018100240W WO 2019095751 A1 WO2019095751 A1 WO 2019095751A1
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cellulose
dimensional
composite hydrogel
layered material
network structure
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French (fr)
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张晗
邢晨阳
陈世优
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深圳大学
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    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape

Definitions

  • the invention belongs to the field of hydrogel preparation, and in particular relates to a cellulose/two-dimensional layer material composite hydrogel and a preparation method thereof.
  • MXenes Two-dimensional transition metal carbide or carbonitride
  • MXenes Two-dimensional transition metal carbide or carbonitride
  • MXenes exhibits excellent photothermal conversion efficiency under near-infrared light (for example, 808 nm), showing great advantages in photothermal therapy; however, MXenes is not sufficiently dispersible in biological fluids. When sedimentation occurs, there are obvious regional differences in the photothermal effect. Moreover, the structure of MXenes-based materials is too single, and the stability of MXenes in them is poor, and it is easy to be detached, which cannot meet the targeting and persistence required for tumor treatment. Therefore, it is necessary to expand the form of MXenes in the field of biomedicine.
  • Cellulose is the most abundant renewable resource on the earth. It has the advantages of complete biocompatibility and complete biodegradability. However, due to its high crystallinity and intramolecular/intermolecular hydrogen bonding, cellulose is difficult to dissolve and refractory. This has made it difficult to form and shape, which greatly limits the development of cellulose in biomedical materials.
  • the present invention provides a cellulose/two-dimensional layered material composite hydrogel, which has high stability in the composite hydrogel, and the composite hydrogel is in a biological fluid. It has good dispersibility, exhibits high photothermal conversion efficiency, has excellent biocompatibility, biosafety and other excellent properties, and has good mechanical strength, and is expected to be applied in the field of biomedicine.
  • the present invention provides a cellulose/two-dimensional layered material composite hydrogel comprising a three-dimensional network structure of cellulose and two-dimensionally supported in the three-dimensional network structure of the cellulose.
  • a layered material that is a two-dimensional transition metal carbide, nitride or carbonitride (MXenes).
  • the chemical formula of the two-dimensional layered material is M n+1 X n T x , wherein M is a transition metal element, X is a carbon element and/or a nitrogen element, and n is an integer of 1-3.
  • T x represents a surface group, and T may be selected from at least one of O 2 ⁇ , OH ⁇ , F ⁇ and NH 4 + .
  • the two-dimensional layered material is Ti 3 C 2 T x , Ti 2 CT x , (Ti 0.5 , Nb 0.5 ) 2 CT x , (V 0.5 , Cr 0.5 ) 3 C 2 T x , Ta 4 C 3 T x , V 2 CT x , Nb 2 CT x , Nb 4 C 3 T x , (Nb 0.8 , Ti 0.2 ) 4 C 3 T x , (Nb 0.8 , Zr 0.2 ) 4 C 3 T x , Ti 3 CNT
  • x , Mo 2 TiC 2 T x , Mo 2 Ti 2 C 3 T x and Cr 2 TiC 2 T x are examples of x , Ti 3 CNT.
  • the two-dimensional layered material may be a detached or unstripped MXenes material.
  • the two-dimensional layered material is a two-dimensional layered material after liquid phase stripping, and the thickness thereof is on the order of nanometers.
  • the two-dimensional layered material has a thickness of 6-10 nm.
  • the two-dimensional layered material may be referred to as "two-dimensional material nanosheet”.
  • a two-dimensional layered material of nanometer thickness can be more firmly loaded into the cellulose three-dimensional network structure.
  • the number of layers of the two-dimensional layered material is 1-20 layers. More preferably, it is 2-10 layers.
  • the two-dimensional layered material has a transverse dimension of from 60 to 200 nm.
  • the lateral dimension refers to the length or width of the two-dimensional layered material.
  • the interaction between the two-dimensional layered material MXenes is weak, and the pure MXenes gel cannot be built by self-assembly behavior.
  • the two-dimensional layered material MXenes is wound by the three-dimensional network structure formed by the cellulose molecules.
  • a two-dimensional layered material MXenes is loaded into the system to form a cellulose/two-dimensional layered material composite hydrogel.
  • the composite hydrogel significantly improves the dispersibility of the two-dimensional layered material MXenes and prevents agglomeration between MXenes.
  • the cellulose three-dimensional network structure comprises a three-dimensional network structure in which cellulose or a cellulose derivative itself is connected, or a three-dimensional network structure formed by a cellulose and/or a cellulose derivative through a crosslinking agent.
  • the cellulose derivative comprises cellulose modified with at least one of graphene oxide, chitosan, cyclodextrin and gelatin, or carboxylated, silylated cellulose.
  • the crosslinking agent includes at least one of epichlorohydrin and isocyanate, but is not limited thereto.
  • the cellulose three-dimensional network structure has a pore structure with a pore diameter of 40-130 ⁇ m.
  • the pore structure has a pore diameter of 50 to 80 ⁇ m.
  • the composite hydrogel has a water content of 85%-98%.
  • the composite hydrogel has a large water content and is easily dispersed in an aqueous solution or a biological body fluid, and has excellent compatibility with body fluids, which can improve adhesion of the two-dimensional layered material to living cells and tissues. .
  • the mass ratio of the cellulose in the three-dimensional network structure of the cellulose to the two-dimensional layered material is 100: (0.0001 to 50), preferably 100: (0.001 to 10), further preferably 100: (0.001) ⁇ 5), more preferably 100:0.05.
  • the three-dimensional network structure of cellulose is a three-dimensional network structure in which cellulose molecules and a crosslinking agent are crosslinked.
  • the mass ratio of the cellulose to the crosslinking agent in the three-dimensional network structure of the cellulose is 100: (1.372-13.71). It is preferably 100: (4.116 to 13.71), further preferably 100: (4.116 to 6.86).
  • the cellulose is one or more of lignocellulose, bamboo cellulose, wood cellulose pulp, cotton cellulose, microcrystalline cellulose, hydroxyethyl cellulose, carboxymethyl cellulose.
  • the composite hydrogel of the cellulose/two-dimensional layered material provided by the first aspect of the invention has a three-dimensional network structure of cellulose as a carrier, and the three-dimensional network structure stably supports a two-dimensional layered material, thereby improving two-dimensional
  • the dispersibility of the layered material prevents agglomeration of the two-dimensional layered material, expanding the product form of the two-dimensional layered material.
  • the composite hydrogel of the cellulose/two-dimensional layered material has good dispersibility in biological fluid, exhibits excellent characteristics of high photothermal conversion efficiency, complete biocompatibility, biosafety, and the like, and has good properties.
  • the mechanical strength is expected to be applied in the field of biomedicine, especially in the field of cancer treatment.
  • the present invention provides a method for preparing a cellulose/two-dimensional layered material composite hydrogel, comprising the following steps:
  • the two-dimensional layered material being a two-dimensional transition metal carbide, nitride or carbonitride;
  • the cellulose regenerant is added to the cross-linking reaction solution for 30-60 minutes, and then the regenerated cross-linking reactant is placed in water for dialysis to obtain a cellulose/two-dimensional layered material composite hydrogel.
  • the cellulose/two-dimensional layered material composite hydrogel prepared by the above method comprises a cellulose three-dimensional network structure crosslinked by cellulose and a crosslinking agent, and further comprises two supported in the three-dimensional network structure of the cellulose. Dimensional layered material. Further, the surface of the two-dimensional layered material is covered by the cellulose three-dimensional network structure.
  • the mixed solvent is precooled to -15 to -5 °C. This facilitates better dissolution of the cellulose powder.
  • the mixed solvent is pre-cooled to -12 °C.
  • the cellulose powder has a particle size of from 10 to 30 microns.
  • the rotational speed of the vigorous stirring is 7000 to 10000 rpm, and the time of the vigorous stirring is 1 to 3 minutes.
  • the high-speed stirring rotation speed is 7000 to 10000 rpm, and the high-speed stirring time is 1 to 3 minutes.
  • the stirring speed and the stirring time of the vigorous stirring and the high-speed stirring may be the same or different.
  • the crosslinking agent is preferably a substance which is not completely hydrophobic.
  • the crosslinking agent carries at least one of an epoxy group (COC) and an isocyanate group (NCO), such that the functional groups in the crosslinking agent can be combined with the cellulose molecular chain -OH cross-linking reaction occurs.
  • the crosslinking agent is selected from one or more of epichlorohydrin and isocyanate, but is not limited thereto. Further preferably, the crosslinking agent is epichlorohydrin.
  • the hydroxyl functional group (-OH) on the cellulose molecular chain undergoes a nucleophilic reaction with the carbon atom on the epoxy functional group (C-O-C) in the epichlorohydrin, and crosslinks to form a hydrogel system.
  • the ultrasonic treatment has a power of 300-500 W and a time of 10 to 30 minutes.
  • the temperature of the crosslinking reaction is 70 to 85 °C.
  • it can be 72, 75, 78, 80 or 82 °C.
  • the cellulose regeneration liquid is a dilute sulfuric acid solution having a mass fraction of 5% to 10%.
  • the volume ratio of the crosslinking reactant to the dilute sulfuric acid solution is 1: (2-3). Further, the volume of the dilute sulfuric acid solution used is 10 to 15 mL.
  • the cross-linking reactant is a hydrogel of cellulose/crosslinking agent/two-dimensional layered material/sodium hydroxide/urea.
  • the dialysis time is 3-7 days.
  • the purpose of dialysis is mainly to remove strong alkali, urea and regenerant.
  • the mass concentration of the strong base is 5-15%, and the mass concentration of urea is 10-15%.
  • the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the mass ratio of the mixed solvent to the cellulose in the cellulose solution is 100: (1 to 4).
  • the volume ratio of the volume of the cellulose solution to the crosslinking agent is 100: (0.2-2.0).
  • the mass ratio of the volume of the cellulose solution to the crosslinking agent is 100: (0.236-2.36) mL/g.
  • the mass ratio of the mass of the cellulose solution to the crosslinking agent is 100: (0.212-2.12).
  • the mass ratio of the cellulose to the two-dimensional transition metal carbide nanosheet is 100: (0.0001 to 50).
  • it may be 100:0.01, 100:0.03, 100:0.05, 100:0.1, 100:0.5, 100:1, 100:5, 100:10.
  • It is preferably 100: (0.001 to 10), more preferably 100: (0.001 to 5), still more preferably 100: 0.05.
  • the two-dimensional layered material MXenes can generate heat under the illumination of near-infrared light (such as 808 nm), and the temperature can be raised from room temperature to up to 150 ° C, and can be killed by regulating its content in the composite hydrogel.
  • the required temperature of dead cancer cells such as 43-60 ° C
  • other common photothermal reagents such as nano gold, nano Pd, CuS and porphyrin
  • the two-dimensional layered material MXenes has higher light Thermal conversion efficiency as well as better biocompatibility and biosafety.
  • the mass ratio of the cellulose to the two-dimensional layered material is 100: (0.0001-0.01).
  • the composite hydrogel can be irradiated with an 808 nm laser having an irradiation power of 0.5/cm 2 , and the photothermal equilibrium temperature reaches 50.2-60.2 ° C, so that the composite hydrogel can have an irradiation power of 1.0/ Under the illumination of 808 nm laser of cm 2 , the photothermal equilibrium temperature reached 55.4-73.1 °C. It can be seen that when the two-dimensional layered material of lower quality is contained, the composite hydrogel can be given a good photothermal effect of killing tumor cells.
  • the two-dimensional layered material MXenes may be an unstripped MXenes bulk material, and may directly perform the A element (such as the Al element) in the layered precursor MAX (chemical formula M n+1 AX n ). Acid etching, high temperature etching or vapor phase etching.
  • the two-dimensional layered material MXenes may also be obtained by further stripping the MXenes bulk material.
  • the two-dimensional layered material has a thickness of 6-10 nm.
  • the two-dimensional layered material may be referred to as a "two-dimensional material nanosheet.”
  • the number of layers of the two-dimensional layered material is from 1 to 20 layers, further preferably from 2 to 10 layers.
  • the two-dimensional layered material has a transverse dimension of from 60 to 200 nm.
  • the lateral dimension refers to the length or width of the two-dimensional layered material.
  • the preparation method of the two-dimensional material nanosheet is not limited, and may be prepared in the following manner:
  • the ratio of the mass of the two-dimensional layered material body to the total volume of the organic solvent is (0.25-1) mg/mL.
  • the milling time is 20-60 min and the milling is carried out under anaerobic conditions.
  • the surface energy of the organic solvent matches the surface energy of the two-dimensional layered material body, and there is a certain interaction between the two to balance the energy required to peel off the two-dimensional layered material body.
  • the organic solvent is selected from the group consisting of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N-cyclohexyl-2-pyrrolidone (CHP), and One or more of isopropyl alcohol (IPA), but is not limited thereto.
  • the low speed centrifugation has a rotational speed of 5000-8000 rpm and a time of 20-40 min. Further preferably, the low speed centrifugal speed is 6000-8000 rpm.
  • the high speed centrifugation has a rotational speed of 15000-18000 rpm for a period of 30-60 min. Further preferably, the high speed centrifugation is 16000-18000 rpm.
  • the vacuum drying has a drying temperature of 50-80 ° C and a drying time of 12-24 h.
  • the formation mechanism of the cellulose/two-dimensional layered material composite hydrogel provided by the invention is as follows: 1) Firstly, the cellulose is dissolved by using a low-temperature alkaline mixed solvent of sodium hydroxide, urea and water to dissolve the cellulose. The hydrogen bond network between the chains is gradually opened to form the sodium and hydroxide ions of the hydrate, forming a new hydrogen bond network with the molecular chain of the cellulose, and the urea molecule hydrate prevents the self of the cellulose molecular chain.
  • the cellulose molecular chain is dissolved in an aqueous solution in the form of a tubular clathrate, which overcomes the high crystallinity and intramolecular/intermolecular strong hydrogen bonding of cellulose which is difficult to dissolve in ordinary water including solvent Solvent problem.
  • the alkaline solution also helps to improve the stability of the two-dimensional transition metal carbide nanosheet and protect the two-dimensional transition metal carbide from oxidation.
  • the two-dimensional layered material is stably supported in a three-dimensional network structure in which cellulose and a crosslinking agent are crosslinked, due to the blocking of the cellulose macromolecular chain,
  • the two-dimensional layered material is in an extremely stable state, and agglomeration sedimentation is less likely to occur, so that the composite hydrogel has a relatively uniform and stable photothermal effect, and the photothermal effect has almost no regional difference.
  • the composite hydrogel contains sufficient moisture to be easily dispersed in an aqueous solution or a biological body fluid, and has excellent compatibility with body fluids, which can improve the two-dimensional layered material and biological cells and tissues. Adhesion.
  • the composite hydrogel when used as an anticancer therapeutic system, it can be directly injected into a tumor site by means of "intratumoral injection".
  • the cellulose-based gel framework of the composite hydrogel can also fix other hydrophilic anticancer drugs, and provide multi-mode comprehensive treatment for targeted therapy, photothermal therapy and chemotherapy of tumor cells.
  • the composite hydrogel since the cellulose and the two-dimensional layered material are both biocompatible materials, the composite hydrogel also has excellent properties such as complete biocompatibility and biosafety.
  • the preparation method of the cellulose/two-dimensional layer material composite hydrogel provided by the second aspect of the invention has the advantages of simple process, green environmental protection, excellent performance and stable uniformity.
  • TEM 1 is a transmission electron microscope (TEM) photograph of a Ti 3 C 2 T x nanosheet used in an embodiment of the present invention: (a) a low resolution photograph (scale is 100 nm); (b) a high resolution topography photograph (the scale is 20 nm); (c) Selected area electron diffraction photographs.
  • TEM transmission electron microscope
  • FIG. 2 is a macro photograph of the aqueous solution of Ti 3 C 2 T x nanosheets provided in the present invention at room temperature for 24 hours before (a), after (b), and the cellulose hydrogel of Comparative Example 4 and Examples Macroscopic photo (c) of a composite hydrogel of cellulose/Ti 3 C 2 T x nanosheets in 2, 4, 6 and 7.
  • Figure 3 is a scanning electron microscope (SEM) photograph of the aerogel obtained after freeze-drying of a hydrogel: (a) aerogel corresponding to cellulose hydrogel (Comparative Example 4); (b) Cellulose/Ti A composite hydrogel of 3 C 2 T x nanosheets (Example 4) corresponds to an aerogel.
  • SEM scanning electron microscope
  • a method for preparing a composite hydrogel of cellulose/small layer Ti 3 C 2 T x nanosheets comprising:
  • Step (1) Preparation of a small layer of Ti 3 C 2 T x nanosheet by liquid phase stripping method, the specific steps are as follows:
  • the resulting etching mixture was centrifuged at 17,000 rpm for 35 minutes, and a solid precipitate was collected and washed repeatedly with absolute ethanol and deionized water until the solution was neutral.
  • the precipitate obtained after washing is a binary multilayer Ti 3 C 2 T x ; finally, the obtained precipitate is dried under vacuum for 48 to 64 hours, and is used;
  • Step (2) Preparing an alkaline aqueous solution of transparent and uniform cellulose, the specific steps of which are as follows:
  • Step (3) Preparation of a composite hydrogel of cellulose/less Ti 3 C 2 T x nanosheets, the specific steps of which are as follows:
  • the composite hydrogel of the cellulose/small layer Ti 3 C 2 T x nanosheet prepared by the embodiment of the invention comprises a three-dimensional network structure formed by crosslinking the cellulose molecule and the crosslinking agent, and is loaded in the three-dimensional network structure.
  • a composite hydrogel prepared from cellulose/small layer Ti 3 C 2 T x nanosheets differs from Example 1 in that, in step 3-a), cellulose and a small layer of Ti 3 C 2 T x nanosheets The mass ratio is 100:0.01.
  • a composite hydrogel prepared from cellulose/small layer Ti 3 C 2 T x nanosheets differs from Example 1 in that, in step 3-a), cellulose and a small layer of Ti 3 C 2 T x nanosheets
  • the mass ratio is 100:0.03.
  • the composite hydrogel for preparing cellulose/less Ti 3 C 2 T x nanosheets differs from Example 1 in the quality of cellulose and less Ti 3 C 2 T x nanosheets in step 3-a) The ratio is 100:0.05.
  • the composite hydrogel for preparing cellulose/less Ti 3 C 2 T x nanosheets differs from Example 1 in the quality of cellulose and less Ti 3 C 2 T x nanosheets in step 3-a) The ratio is 100:5.
  • the composite hydrogel for preparing cellulose/less Ti 3 C 2 T x nanosheets differs from Example 1 in the quality of cellulose and less Ti 3 C 2 T x nanosheets in step 3-a) The ratio is 100:10.
  • the composite hydrogel for preparing cellulose/less Ti 3 C 2 T x nanosheets differs from Example 1 in the quality of cellulose and less Ti 3 C 2 T x nanosheets in step 3-a) The ratio is 100:50.
  • Step (1) Preparing an alkaline aqueous solution of transparent and uniform cellulose, the specific steps are as follows:
  • Step (2) Preparation of a cellulose hydrogel, the specific steps of which are as follows:
  • Comparative Example 2 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:2, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:4.
  • Comparative Example 3 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:3, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:6.
  • Comparative Example 4 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:4, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:10.
  • Comparative Example 5 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:4, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:14.
  • Comparative Example 6 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:4, and the volume ratio of the cellulose solution to the epichlorohydrin was 100:20.
  • FIG. 1 is a transmission electron microscope microtopography of a small layer of Ti 3 C 2 T x nanosheets used in an embodiment of the present invention, (a) being a low resolution photograph; and (b) being a high resolution photograph.
  • the microscopic morphology of the less Ti 3 C 2 T x nanosheets was tested as follows: Apparatus: High resolution transmission electron microscope; Model: FEI Tecnai G 2 F30; Test high pressure: 300 kV.
  • the size of the small-layer Ti 3 C 2 T x nanosheet is about 60 nm ⁇ 200 nm; as shown in (b) of FIG. 1, a small layer of Ti 3 C 2 T x nanosheets is shown.
  • a distinct plurality of layered structures indicate that the lesser Ti 3 C 2 T x nanosheets of the present invention have a better two-dimensional layered structure.
  • the number of layers of the obtained small-layer Ti 3 C 2 T x nanosheets is 6 to 10 layers.
  • the obtained small-layer Ti 3 C 2 T x nanosheet has a weak selective electron diffraction structure, indicating that the small-layer Ti 3 C 2 T x nanosheet has a certain crystal structure.
  • Figure 2 provides a macro photograph of the resulting aqueous solution (100 ppm) of a small layer of Ti 3 C 2 T x nanosheets placed at room temperature for 24 hours, and the cellulose hydrogel and cellulose/less Ti 3 C of Comparative Example 4 Macroscopic photograph of a composite hydrogel of 2 T x nanosheets (Examples 2, 4, 6 and 7). It can be seen from Fig. 2 that the small layer of Ti 3 C 2 T x nanosheet aqueous solution is uniformly dispersed 24 hours ago (Fig. 2 (a)); however, after standing for 24 hours, a small amount of Ti 3 C 2 T x nanosheet aqueous solution is obtained. Significant sedimentation behavior occurred, and the color of the solution became lighter (Fig.
  • Figure 3 provides a composite hydrogel of cellulose hydrogel ((a), Comparative Example 4) and cellulose/less Ti 3 C 2 T x nanosheets ((b), Example 4) after freeze drying A scanning electron micrograph of the corresponding aerogel obtained.
  • the test conditions were as follows: To test the macromolecular porous structure in the cellulose hydrogel, the tested hydrogel (the cellulose hydrogel of Comparative Example 4 and the cellulose/less Ti 3 C 2 T x nm of Example 4) The composite hydrogel of the tablet was first subjected to freeze-drying treatment to obtain a corresponding aerogel structure, wherein the experimental conditions of freeze-drying were: temperature: -80 ° C; time: 72 hours. Then the microtopography was tested, the instrument equipment used: cold field emission scanning electron microscope; model: SEM-Hitachi SU8010; test voltage: 3kV; sample surface silver time: 20 seconds.
  • both types of aerogels exhibit significant porosity, which is determined by the three-dimensional gel network structure of cellulose.
  • the composite hydrogel of the cellulose/small layer Ti 3 C 2 T x nanosheet prepared by the invention has a uniform pore structure distribution, and the pore diameter is 50-80 ⁇ m, and the porosity is obtained. About 75%.
  • Table 1 shows typical compositions and physical properties of Comparative Examples 1-6 and Examples 1-7 of the present invention. As is apparent from Table 1, in Comparative Examples 1 to 6, as the volume fraction of the crosslinking agent epichlorohydrin was increased, the mechanical strength of the finally obtained cellulose hydrogel was also remarkably increased.
  • the compression modulus is 19.4 kPa; when the volume ratio of cellulose solution to epichlorohydrin is increased to 100:1.0 (i.e., Comparative Example 4) and 100:2.0 (i.e., Comparative Example 6), their respective compressive moduli increased to 60.8 kPa and 79.1 kPa, respectively, due to the higher cross-linking agent content of the cellulose hydrogel.
  • the degree of chemical cross-linking is greatly increased.
  • pure cellulose hydrogel lacks any functionality and does not exhibit any photothermal effect, and its photothermal equilibrium temperature is 25 ° C, which is substantially the same as room temperature.
  • the final photothermal equilibrium temperature of the composite hydrogel can be 0.5 and 1.0 W/cm 2 . Reaching 50.2 and 55.4 ° C, respectively, has an increase of about 25.2 and 30.4 ° C compared to a pure cellulose hydrogel.
  • the equilibrium temperature of the photothermal even more than the substantial increase
  • the detection range of the thermal imager For example, when the mass ratio of cellulose to a small number of Ti 3 C 2 T x nanosheets is 100:5 (ie, Example 5), the final photothermal equilibrium temperature of the composite hydrogel is 0.5 and 1.0 W/cm 2 , respectively.
  • the final light of the composite hydrogel when the mass ratio of cellulose to the small layer of Ti 3 C 2 T x nanosheets is 100:10 (ie, Example 6) and 100:50 (ie, Example 7)
  • the heat balance temperature is higher than 150 ° C, which exceeds the detection range of the thermal imager.

Abstract

本发明提供了一种纤维素/二维层状材料复合水凝胶，所述复合水凝胶包括纤维素三维网络结构、以及负载在所述纤维素三维网络结构中的二维材料，所述二维层状材料为二维过渡金属碳化物、氮化物或碳氮化物。二维层状材料可被稳定地负载在该复合水凝胶体系中，不易团聚，所述复合水凝胶与生物体液的相容性好，且具有完全生物可降解性、高生物安全性，可用于生物医学领域。本发明还提供了该复合水凝胶的制备方法。

Description

一种纤维素/二维层状材料复合水凝胶及其制备方法
本申请要求于2017年11月15日提交中国专利局、申请号为201711128428.4、发明名称为“一种纤维素/二维层状材料复合水凝胶及其制备方法”的中国专利申请的优先权，上述在先申请的内容以引入的方式并入本文本中。
技术领域
本发明属于水凝胶制备领域，具体涉及一种纤维素/二维层状材料复合水凝胶及其制备方法。
背景技术
二维过渡金属碳化物或碳氮化物(即MXenes)，是今年来发现的一种新型二维材料，它具有高比表面积、高电导率等特点，又具备组分灵活可调，最小纳米层厚可控等优势，在储能、电磁屏蔽、水处理、气体/生物传感以及光电化学催化等领域拥有巨大潜力。为强调其与石墨烯(graphene)类似的二维结构，这一类化合物统一命名为MXenes。
在生物医学领域中，MXenes表现出优异的近红外光(例如808nm)下的光热转换效率，在光热治疗中显示出极大的优势；然而，MXenes在生物体液中的分散性不足，易发生沉降，其光热效果存在明显的地域性差异。而且目前以MXenes为基础的材料的结构过于单一，且MXenes在其中的稳定性较差，容易游离出来，无法满足肿瘤治疗过程所需的靶向性和持久性。因此，有必要拓展MXenes在生物医学领域中的存在形式。
纤维素是地球上最丰富的可再生资源，具有完全生物相容性、完全生物降解性等优点，但受其高结晶性和分子内/分子间氢键的制约，纤维素难溶难熔，导致难以加工成型，这极大限制了纤维素在生物医用材料中的发展。
发明内容
鉴于此，本发明提供一种纤维素/二维层状材料复合水凝胶，二维层状材料在该复合水凝胶中的稳定性较高，所述复合水凝胶在生物体液中的分散性较好，表现出高光热转换效率，具有完全生物相容性、生物安全性等优异特性，并具有较好的力学强度，有望应用在生物医学领域中。
第一方面，本发明提供了一种纤维素/二维层状材料复合水凝胶，所述复合水凝胶包括纤维素三维网络结构、以及负载在所述纤维素三维网络结构中的二维层状材料，所述二维层状材料为二维过渡金属碳化物、氮化物或碳氮化物(MXenes)。
其中，所述二维层状材料(MXenes)的化学式为M n+1X nT x，其中，M为过渡金属元素，X为碳元素和/或氮元素，n为1-3的整数，T x表示表面基团，T可选自O 2-、OH -、F -和NH 4 +中的至少一种。
进一步地，所述二维层状材料为Ti 3C 2T x、Ti 2CT x、(Ti 0.5，Nb 0.5) 2CT x、(V 0.5，Cr 0.5) 3C 2T x、Ta 4C 3T x、V 2CT x、Nb 2CT x、Nb 4C 3T x、(Nb 0.8，Ti 0.2) 4C 3T x、(Nb 0.8，Zr 0.2) 4C 3T x、Ti 3CNT x、Mo 2TiC 2T x、Mo 2Ti 2C 3T x和Cr 2TiC 2T x中的一种或多种。
本发明中，所述二维层状材料可以为剥离或未经剥离的MXenes材料。优选地，所述二维层状材料为经液相剥离后的二维层状材料，其厚度为纳米级。
优选地，所述二维层状材料的厚度为6-10nm。此时，可把所述二维层状 材料称为“二维材料纳米片”。纳米级厚度的二维层状材料可以更牢固地负载进所述纤维素三维网络结构中。
其中，所述二维层状材料的层数为1-20层。进一步优选为2-10层。
优选地，所述二维层状材料的横向尺寸为60-200nm。所述横向尺寸是指二维层状材料的长度或宽度。
二维层状材料MXenes之间的相互作用较弱，无法通过自组装行为来搭建纯MXenes的凝胶，本发明中主要借助纤维素分子形成的三维网络结构，将二维层状材料MXenes缠绕到该纤维素三维网络结构中，使二维层状材料MXenes负载到该体系中，形成纤维素/二维层状材料复合水凝胶。其中，所述复合水凝胶显著提高了二维层状材料MXenes的分散性，阻止了MXenes之间的团聚。
其中，所述纤维素三维网络结构包括纤维素或纤维素衍生物自身连接成的三维网络结构，或者为纤维素和/或纤维素衍生物通过交联剂形成的三维网络结构。
其中，所述纤维素衍生物包括经氧化石墨烯、壳聚糖、环糊精和明胶中的至少一种所改性的纤维素，或羧基化、硅烷化的纤维素。
优选地，所述交联剂包括环氧氯丙烷和异氰酸酯中的至少一种，但不限于此。
其中，所述纤维素三维网络结构具有孔径为40-130μm的孔隙结构。优选地，所述孔隙结构的孔径为50-80μm。
其中，所述复合水凝胶的含水量为85％-98％。该复合水凝胶的含水量较大，易于分散在水溶液或生物体体液中，与体液具有优异的相容性，这可提高 所述二维层状材料与生物体细胞和组织的粘附性。
其中，所述纤维素三维网络结构中的纤维素与所述二维层状材料的质量比为100：(0.0001～50)，优选为100：(0.001～10)，进一步优选为100：(0.001～5)，更优选为100：0.05。
在本发明一实施方式中，所述纤维素三维网络结构为纤维素分子与交联剂交联成的三维网络结构。
其中，所述纤维素三维网络结构中的纤维素与交联剂的质量比为100：(1.372-13.71)。优选为100：(4.116-13.71)，进一步优选为100：(4.116-6.86)。
其中，所述纤维素为木质纤维素、竹纤维素、木纤维素浆粕、棉花纤维素、微晶纤维素、羟乙基纤维素、羧甲基纤维素中的一种或多种。
本发明第一方面提供的纤维素/二维层状材料的复合水凝胶，其以纤维素三维网络结构为载体，该三维网络结构中稳定地负载有二维层状材料，提高了二维层状材料的分散性，阻止了二维层状材料的团聚，拓展了所述二维层状材料的产品形式。所述纤维素/二维层状材料的复合水凝胶在生物体液中的分散性较好，表现出高光热转换效率、完全生物相容性、生物安全性等优异特性，并具有较好的力学强度，有望应用在生物医学领域中，尤其是用于肿瘤治疗领域。
第二方面，本发明提供了一种纤维素/二维层状材料复合水凝胶的制备方法，包括以下步骤：
(1)提供二维层状材料，所述二维层状材料为二维过渡金属碳化物、氮化物或碳氮化物；
(2)配制含强碱、尿素和水的混合溶剂，并进行预冷，将纤维素粉末加 入到预冷后的所述混合溶剂中，剧烈搅拌，得到纤维素溶液；
(3)在高速搅拌条件下，将所述二维层状材料、交联剂与所述纤维素溶液相混合，超声处理后，于65-90℃下进行交联反应0.5-2小时，得到交联反应物；
(4)向所述交联反应物中加入纤维素再生液浸泡30-60min，之后将再生后的交联反应物置于水中进行透析，得到纤维素/二维层状材料复合水凝胶。
采用上述方法制得的纤维素/二维层状材料复合水凝胶，包括纤维素和交联剂交联成的纤维素三维网络结构，还包括负载在所述纤维素三维网络结构中的二维层状材料。进一步地，所述二维层状材料的表面被所述纤维素三维网络结构所覆盖。
其中，步骤(2)中，所述混合溶剂被预冷至-15～-5℃。这样有利于所述纤维素粉末的更好溶解。优选地，所述混合溶剂被预冷至-12℃。
可选地，所述纤维素粉末的粒径为10-30微米。
其中，步骤(2)中，所述剧烈搅拌的转速为7000～10000rpm，所述剧烈搅拌的时间为1～3分钟。
其中，步骤(3)中，所述高速搅拌的转速为7000～10000rpm，所述高速搅拌的时间为1～3分钟。所述剧烈搅拌与所述高速搅拌的搅拌转速、搅拌时间可以相同，也可以不同。
步骤(3)中，所述交联剂最好为不完全疏水的物质。所述交联剂中带有环氧基(C-O-C)和异腈酸酯基(NCO)中的至少一种，这样所述交联剂中的这些官能团就能与所述纤维素分子链中的-OH发生交联反应。
优选地，所述交联剂选自环氧氯丙烷和异氰酸酯中的一种或多种，但不限 于此。进一步优选地，所述交联剂为环氧氯丙烷。此时，纤维素分子链上的羟基官能团(-OH)会与环氧氯丙烷中环氧官能团(C-O-C)上的碳原子发生亲核反应，交联形成水凝胶体系。
其中，步骤(3)中，所述超声处理的功率为300-500W，时间为10～30分钟。
优选地，步骤(3)中，所述交联反应的温度为70-85℃。例如可以是72、75、78、80或82℃。
其中，步骤(4)中，所述纤维素再生液为质量分数为5％～10％的稀硫酸溶液。
优选地，所述交联反应物与所述稀硫酸溶液的体积比为1：(2-3)。进一步地，所用稀硫酸溶液的体积为10～15mL。其中，交联反应物为纤维素/交联剂/二维层状材料/氢氧化钠/尿素的水凝胶。
其中，步骤(4)中，所述透析的时间为3-7天。透析的目的主要是为了除去强碱、尿素及再生液。
其中，步骤(2)中，所述混合溶剂中，强碱的质量浓度为5-15％，尿素的质量浓度为10-15％。
其中，所述强碱为氢氧化钠、氢氧化钾和氢氧化锂中的一种或多种。
其中，步骤(2)中，所述纤维素溶液中，混合溶剂与纤维素的质量比为100：(1～4)。
优选地，所述纤维素溶液的体积与所述交联剂的体积比为100：(0.2-2.0)。
优选地，所述纤维素溶液的体积与所述交联剂的质量比为100：(0.236-2.36)mL/g。
优选地，所述纤维素溶液的质量与所述交联剂的质量比为100：(0.212-2.12)。
其中，所述纤维素与二维过渡金属碳化物纳米片的质量比为100：(0.0001～50)。例如可以是100：0.01，100：0.03，100：0.05，100：0.1，100：0.5，100：1，100：5，100：10。优选为100：(0.001～10)，进一步优选为100：(0.001～5)，更优选为100：0.05。
所述二维层状材料MXenes可在近红外光(如808nm)照射下产生热量，温度可从室温升至高达150℃，通过调控其在所述复合水凝胶中的含量，可达到杀死癌细胞的所需温度(如43-60℃)，与其他常见的光热试剂(例如纳米金、纳米Pd、CuS及卟啉等)相比，二维层状材料MXenes具有较高的光热转换效率以及较好的生物相容性和生物安全性。
可选地，所述纤维素与所述二维层状材料的质量比为100：(0.0001-0.01)。此时，可使所述复合水凝胶在辐照功率为0.5/cm 2的808nm激光照射下，光热平衡温度达到50.2-60.2℃，可使所述复合水凝胶在辐照功率为1.0/cm 2的808nm激光照射下，光热平衡温度达到55.4-73.1℃。可见，含有较低质量的二维层状材料时，就能赋予所述复合水凝胶良好的杀伤肿瘤细胞的光热效果。
本发明中，所述二维层状材料MXenes可以是未经剥离的MXenes本体材料，可以直接对层状前驱体MAX(化学式为M n+1AX n)中的A元素(如Al元素)进行酸刻蚀、高温刻蚀或气相刻蚀得到。所述二维层状材料MXenes还可以是对MXenes本体材料进行进一步剥离后获得。
优选地，所述二维层状材料的厚度为6-10nm。此时，可把所述二维层状材料称为“二维材料纳米片”。
优选地，所述二维层状材料的层数为1-20层，进一步优选为2-10层。
优选地，所述二维层状材料的横向尺寸为60-200nm。所述横向尺寸是指二维层状材料的长度或宽度。
本发明中，所述二维材料纳米片的制备方式不限，可以是采用如下方式制备得到：
(a)将氢氟酸和层状前驱体MAX(化学式为M n+1AX n)进行缓慢混合，以所述层状前驱体MAX中的A位元素刻蚀掉，得到刻蚀混合液；
对所述刻蚀混合液进行离心后，洗涤、收集固体沉淀，对所述固体沉淀进行真空干燥后，得到二维层状材料本体(即为MXenes)；
(b)将上述二维层状材料本体和有机溶剂混合后进行研磨，向研磨所得混合物中补加所述有机溶剂，得到分散液；将所述分散液在功率为1000～1400W下进行探针式超声30-60小时，对超声后所得溶液进行低速离心，收集上清液，并将所述上清液高速离心后，收集固体沉淀，所述固体沉淀经真空干燥，得到所述二维材料纳米片。
可选地，所述二维层状材料本体的质量与所述有机溶剂的总体积之比为(0.25-1)mg/mL。
可选地，所述研磨的时间为20-60min，所述研磨是在无氧条件下进行。
所述有机溶剂的表面能与二维层状材料本体的表面能相匹配，二者之间存在一定的相互作用平衡了剥离该二维层状材料本体所需要的能量。其中，所述有机溶剂选自N-甲基吡咯烷酮(NMP)、二甲亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、N-环己基-2-吡咯烷酮(CHP)和异丙醇(IPA)中的一种或多种，但不限于此。
优选地，所述低速离心的转速为5000-8000rpm，时间为20-40min。进一步优选地，所述低速离心的转速为6000-8000rpm。
优选地，所述高速离心的转速为15000-18000rpm，时间为30-60min。进一步优选地，所述高速离心的转速为16000-18000rpm。
优选地，所述真空干燥的干燥温度为50-80℃，干燥时间为12-24h。
本发明提供的纤维素/二维层状材料复合水凝胶的形成机理为：1)首先，采用氢氧化钠、尿素和水的低温碱性混合溶剂来溶解纤维素，可将纤维素的分子链之间的氢键网络被逐渐打开，形成水合物的钠离子和氢氧根离子，与纤维素的分子链形成新的氢键网络，而尿素分子水合物又阻止了纤维素分子链的自缔合，最终纤维素分子链以管状包合物的形式溶解于水溶液中，这克服了高结晶性和分子内/分子间较强氢键的纤维素较难溶解在包括水溶剂在内的普通溶剂的问题。此外，碱性溶液也有助于提高二维过渡金属碳化物纳米片的稳定性、保护二维过渡金属碳化物以防其被氧化。2)当将纤维素水溶液与二维层状材料、交联剂在高速搅拌下混合、超声后，在一定温度下，纤维素分子链和交联剂发生亲核反应，同时将二维层状材料嵌合进来，使二维层状材料处于极为稳定的状态，形成三维网状结构的纤维素/交联剂/二维层状材料/氢氧化钠/尿素的水凝胶。3)所述纤维素/交联剂/二维层状材料/氢氧化钠/尿素的水凝胶在经过稀硫酸溶液的浸泡后，纤维素发生再生现象，即纤维素分子链发生析出现象，便于再生后的水凝胶取出，经过水的浸泡后，氢氧化钠和尿素可被除去，最终得到纤维素/二维层状材料的复合水凝胶。
所述纤维素/二维层状材料的复合水凝胶中，二维层状材料被稳定负载在纤维素和交联剂交联成的三维网络结构中，由于纤维素大分子链的阻拦，二维 层状材料处于极为稳定的状态，不易发生团聚沉降，使得所述复合水凝胶具有较均匀、稳定的光热效果，其光热效果几乎不存在地域性差别。其次，该复合水凝胶中包含了充足的水分，易于分散在水溶液或生物体体液中，与体液具有优异的相容性，这可提高所述二维层状材料与生物体细胞和组织的粘附性。再者，由于所述复合水凝胶的凝胶性，在用作抗癌治疗体系时，可以通过“瘤内注射”的方式，将其直接注射到肿瘤部位。此外，该复合水凝胶中以纤维素为主体的凝胶框架还可以固定其他亲水性抗癌药物，赋予其实现对肿瘤细胞的靶向治疗、光热治疗以及化学治疗的多模式综合治疗。最后，由于所述纤维素、二维层状材料均是生物相容性好的材料，使所述复合水凝胶也具有完全生物相容性、生物安全性等优异特性。
本发明第二方面提供的纤维素/二维层状材料复合水凝胶的制备方法，工艺简单，绿色环保，所得产品性能优异，稳定均一。
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明实施例中采用的Ti 3C 2T x纳米片的透射电子显微镜(TEM)照片：(a)低分辨照片(标尺为100nm)；(b)高分辨形貌照片(标尺为20nm)；(c)选区电子衍射照片。
图2为本发明中提供的Ti 3C 2T x纳米片的水溶液在室温下放置24小时前(a)、后(b)的宏观照片，以及对比例4的纤维素水凝胶与实施例2,4,6和7中纤维素/Ti 3C 2T x纳米片的复合水凝胶的宏观实物照片(c)。
图3为水凝胶经冷冻干燥后所得气凝胶的扫描电子显微镜(SEM)照片：(a)为纤维素水凝胶(对比例4)对应的气凝胶；(b)纤维素/Ti 3C 2T x纳米片的复合水凝胶(实施例4)对应的气凝胶。
具体实施方式
以下所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。其中，本发明实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。
若无特别说明，本发明实施例采用的原料及其它化学试剂皆为市售商品。
实施例1
一种纤维素/少层Ti 3C 2T x纳米片的复合水凝胶的制备方法，包括：
步骤(1).通过液相剥离法制备少层Ti 3C 2T x纳米片，其具体步骤如下：
1-a):通过氢氟酸腐蚀法来制备多层Ti 3C 2T x材料，料具体操作如下：将粉状三元层状氮化物Ti 3AlC 2和氢氟酸水溶液(HF的质量分数为10％～40％)按固含量比为10g/100mL加入到聚乙烯塑料烧杯中进行反应。其中，三元层状氮化物Ti 3C 2T x需要缓慢加入到氢氟酸水溶液中，缓慢加入的时间为10分钟～30分钟，加入完毕后，于反应温度下反应12小时～24小时。反应结束后，对所得刻蚀混合液在17000rpm的转速下离心35分钟，收集固体沉淀，并对其反复用无 水乙醇和去离子水进行洗涤，直到溶液呈中性。洗涤后得到的沉淀即为二元多层Ti 3C 2T x；最后将所得沉淀在真空干燥48～64小时，待用；
1-b):将上述二维多层Ti 3C 2T x MXene材料和N-甲基吡咯烷酮(NMP)按固含量比为500mg/10mL加入到玛瑙研钵里进行机械研磨，时间为30分钟；将研磨所得的复合物移至100mL反应瓶中，并加入90mL的NMP，得到分散液，二维多层Ti 3C 2T x MXene材料在总的NMP中的固含量为5mg/mL。
1-c):将上述分散液进行探针超声，超声功率为600W，时间为50小时，得到含二维少层Ti 3C 2T x纳米片的溶液，即少层Ti 3C 2T x纳米片与NMP的混合溶液，待用。
1-d):将上述少层Ti 3C 2T x纳米片溶液进行离心，转速为7000rpm，时间为25分钟，缓慢取出3/4的上清液。
1-e):然后对上述上清液进行高速离心，转速为17000rpm，时间为35分钟，缓慢倒出上清液，收集少层Ti 3C 2T x纳米片固体。
1-f):将上述少层Ti 3C 2T x纳米片固体在真空干燥箱里干燥20小时，温度为75℃，最终得到干燥的少层Ti 3C 2T x纳米片固体，待用。
步骤(2).制备透明均一的纤维素的碱性水溶液，其具体步骤如下：
2-a):将氢氧化钠、尿素以及去离子水按照质量比为7％/12％/81％的比例加入到200mL的烧杯中，得到混合溶剂，其中去离子水的质量为81.0g，即，混合溶剂的总体积为100mL；将混合溶剂进行预冷30分钟，使其温度达到-12℃，待用。
2-b):将纤维素粉末加入到上述预冷后的混合溶剂中，其中混合溶剂与纤维素的质量比为100：4；接着将得到的纤维素悬浮液进行剧烈搅拌，搅拌速度为 7500rpm，时间为2分钟，最终得到均一、透明的纤维素溶液，即，纤维素/氢氧化钠/尿素/去离子水的混合溶液，待用。
步骤(3).制备纤维素/少层Ti 3C 2T x纳米片的复合水凝胶，其具体步骤如下：
3-a):取步骤(2)中的纤维素溶液5mL，取步骤(1)中的少层Ti 3C 2T x纳米片固体，其中纤维素与少层Ti 3C 2T x纳米片的质量比为100：0.0001，取环氧氯丙烷0.5mL，即纤维素溶液与环氧氯丙烷的体积之比为100：10；将三者高度搅拌，搅拌速度为7500rpm，时间为2分钟；接着水浴超声，超声功率300W，时间为15分钟，得到超声后的混合液，即，纤维素/环氧氯丙烷/少层Ti 3C 2T x纳米片/氢氧化钠/尿素/去离子水的混合溶液。
3-b):将上述超声后的混合液置于70℃的油浴中进行化学交联反应，反应时间为1.5小时，得到交联反应物，即，纤维素/环氧氯丙烷/少层Ti 3C 2T x纳米片/氢氧化钠/尿素/去离子水的水凝胶。
3-c):向上述交联反应物中加入15mL、质量分数为8％的稀硫酸溶液，酸浸泡40分钟，以使纤维素再生行为，即，纤维素分子链发生析出。接着，将再生后的交联反应物置于去离子水中，透析5天，以使氢氧化钠、尿素、硫酸逐渐透析出来，最终得到纤维素/少层Ti 3C 2T x纳米片的复合水凝胶。
本发明实施例制得的纤维素/少层Ti 3C 2T x纳米片的复合水凝胶，包括纤维素分子与交联剂交联成的三维网络结构，以及负载在该三维网络结构中的少层Ti 3C 2T x纳米片。
实施例2
制备纤维素/少层Ti 3C 2T x纳米片/的复合水凝胶，与实施例1的区别在于， 步骤3-a)中，纤维素与少层Ti 3C 2T x纳米片的质量比为100：0.01。
实施例3
制备纤维素/少层Ti 3C 2T x纳米片/的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与少层Ti 3C 2T x纳米片的质量比为100：0.03。
实施例4
制备纤维素/少层Ti 3C 2T x纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与少层Ti 3C 2T x纳米片的质量比为100：0.05。
实施例5
制备纤维素/少层Ti 3C 2T x纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与少层Ti 3C 2T x纳米片的质量比为100：5。
实施例6
制备纤维素/少层Ti 3C 2T x纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与少层Ti 3C 2T x纳米片的质量比为100：10。
实施例7
制备纤维素/少层Ti 3C 2T x纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与少层Ti 3C 2T x纳米片的质量比为100：50。
为突出本发明的有益效果，同时提供以下对比实施例：
对比例1
制备纤维素水凝胶，包括:
步骤(1).制备透明均一的纤维素的碱性水溶液，其具体步骤如下：
1-a):将氢氧化钠、尿素以及去离子水按照质量比为7％/12％/81％的比例加 入到200mL的烧杯中，得到混合溶剂，其中去离子水的质量为81.0g，即，混合溶剂的总体积为100mL；将混合溶剂进行预冷30分钟，使其温度达到-12℃，待用。
1-b):将纤维素粉末加入到上述预冷后的混合溶剂中，其中混合溶剂与纤维素的质量比为100：1；接着将得到的纤维素悬浮液进行剧烈搅拌，搅拌速度为7500rpm，时间为2分钟，最终得到均一、透明的纤维素溶液，即，纤维素/氢氧化钠/尿素/去离子水的混合溶液。
步骤(2).制备纤维素水凝胶，其具体步骤如下：
2-a):取步骤(1)中的纤维素溶液5mL，取环氧氯丙烷0.1mL，即纤维素溶液与环氧氯丙烷的体积之比为100：2；将三者高度搅拌，搅拌速度为7500rpm，时间为2分钟；接着水浴超声，超声功率300W，时间为15分钟，得到超声后的混合液，即，纤维素/环氧氯丙烷/氢氧化钠/尿素/去离子水的混合溶液，待用。
2-b):将上述超声后的混合溶液置于70℃的油浴中发生化学交联反应，反应时间为1.5小时，得到交联反应物，即，纤维素/环氧氯丙烷/氢氧化钠/尿素/去离子水的水凝胶，待用。
2-c):向上述交联反应物中加入15mL、质量分数为8％的稀硫酸溶液进行浸泡40分钟，以使纤维素再生行为。接着，将再生后的交联反应物置于去离子水中，透析5天，以使氢氧化钠和尿素逐渐透析出来，最终得到纤维素/环氧氯丙烷的水凝胶，(简称为纤维素水凝胶)。
对比实施例2：与对比实施例1的区别在于，混合溶剂与纤维素的质量比为100：2，纤维素溶液与环氧氯丙烷的体积之比为100：4。
对比实施例3：与对比实施例1的区别在于，混合溶剂与纤维素的质量比为100：3，纤维素溶液与环氧氯丙烷的体积之比为100：6。
对比实施例4：与对比实施例1的区别在于，混合溶剂与纤维素的质量比为100：4，纤维素溶液与环氧氯丙烷的体积之比为100：10。
对比实施例5：与对比实施例1的区别在于，混合溶剂与纤维素的质量比为100：4，纤维素溶液与环氧氯丙烷的体积之比为100：14。
对比实施例6：与对比实施例1的区别在于，混合溶剂与纤维素的质量比为100：4，纤维素溶液与环氧氯丙烷的体积之比为100：20。
图1为本发明实施例中所使用的少层Ti 3C 2T x纳米片的透射电子显微镜微观形貌图，(a)为低分辨照片；(b)为高分辨照片。少层Ti 3C 2T x纳米片的微观形貌测试条件如下：仪器设备：高分辨透射电子显微镜；型号：FEI Tecnai G 2F30；测试高压：300kV。
由图1中(a)可知，少层Ti 3C 2T x纳米片的尺寸约60纳米×200纳米；由图1中(b)可知，少层Ti 3C 2T x纳米片显示出了明显的多个层状结构，表明本发明中少层Ti 3C 2T x纳米片具有较好的二维层状结构。此外，所得少层Ti 3C 2T x纳米片的层数为6～10层。由图1中(c)可知，所得少层Ti 3C 2T x纳米片具有较微弱的选区电子衍射结构，表明少层Ti 3C 2T x纳米片具有一定的晶体结构。
图2提供了所得少层Ti 3C 2T x纳米片的水溶液(100ppm)在室温下放置24小时前后的宏观照片，以及对比例4的纤维素水凝胶和纤维素/少层Ti 3C 2T x纳米片(实施例2，4，6和7)复合水凝胶宏观实物照片。由图2可知，少层Ti 3C 2T x纳米片水溶液在24小时前，分散均匀(图2中(a))；但是静置24小时后，少层 Ti 3C 2T x纳米片水溶液发生显著的沉降行为，溶液颜色变浅(图2中(c))，表明少层Ti 3C 2T x纳米片的水溶性较差。由图2中(c)可知，纯纤维素水凝胶(对比例4)整体呈无色半透明状“果冻型”宏观形貌；而在少层Ti 3C 2T x纳米片成功引入后，所得纤维素/少层Ti 3C 2T x纳米片的复合水凝胶整体随着少层Ti 3C 2T x纳米片含量的增加而呈黑色，二者具有鲜明的颜色对比。
图3提供了纤维素水凝胶((a)，对比例4)和纤维素/少层Ti 3C 2T x纳米片的复合水凝胶((b)，实施例4)在冷冻干燥后所得对应气凝胶的扫描电子显微镜照片。测试条件如下：为保留纤维素水凝胶中的大分子多孔结构，测试的水凝胶(对比例4的纤维素水凝胶和实施例4的纤维素/少层Ti 3C 2T x纳米片的复合水凝胶)首先经过冷冻干燥处理得到相应的气凝胶结构，其中冷冻干燥的实验条件：温度：-80℃；时间：72小时。然后进行微观形貌的测试，采用的仪器设备：冷场发射扫描电子显微镜；型号：SEM-Hitachi SU8010；测试电压：3kV；样品表面渡银时间：20秒。
由图3可知，这两类气凝胶均表现出明显的多孔性，这是由纤维素的三维凝胶网络结构所决定。但较明显的是，本发明制得的纤维素/少层Ti 3C 2T x纳米片的复合水凝胶所对应气凝胶的孔状结构分布较均匀，孔径为50-80μm，气孔率约为75％。
将对比例1～6制得的纤维素/环氧氯丙烷水凝胶与实施例1～7所制备的纤维素/少层Ti 3C 2T x纳米片的复合水凝胶分别进行力学性能测试和光热性能测试，结果如表1所示。
表1 对比例1-6和实施例1-7中水凝胶的基本成分和性能参数
Figure PCTCN2018100240-appb-000001
Figure PCTCN2018100240-appb-000002
表1给出了本发明专利中对比例1-6和实施例1-7的典型组成和物理性能。由表1可知，在对比例1-6中，随着交联剂环氧氯丙烷的体积分数的提高，其最终所得纤维素水凝胶的力学强度基本也是显著地增加。例如，当纤维素溶液与环氧氯丙烷的体积比100：0.2时(即对比例1)，其压缩模量为19.4kPa；当纤维素溶液与环氧氯丙烷的体积比增加至100：1.0(即对比例4)和100：2.0时(即对比例6)时，其相应的压缩模量分别增加至60.8kPa和79.1kPa，这是由于较多的交联剂含量使得纤维素水凝胶的化学交联度大幅提高所致。然而，纯纤维素水凝胶缺乏任何功能性，其并未表现出任何光热效果，其光热平衡温度为25℃，与室温基本相同。
然而，作为强烈的对比，在实施例1-7提供的纤维素/少层Ti 3C 2T x纳米片的 复合水凝胶中，由于少层Ti 3C 2T x纳米片的引入，其最终的光热平衡温度大幅度升高。例如，当纤维素与少层Ti 3C 2T x纳米片的质量比100：0.0001(即实施例1)时，复合水凝胶的最终光热平衡温度在0.5和1.0W/cm 2时就能分别达到50.2和55.4℃，与纯纤维素水凝胶相比，有约25.2和30.4℃的提高。当继续增大纤维素/少层Ti 3C 2T x纳米片的复合水凝胶中少层Ti 3C 2T x纳米片的质量分数时，这一光热平衡温度大幅度增大甚至超过了热成像仪的检测范围。例如，当纤维素与少层Ti 3C 2T x纳米片的质量比100：5(即实施例5)时，复合水凝胶的最终光热平衡温度在0.5和1.0W/cm 2时分别为122和135.7℃；当纤维素与少层Ti 3C 2T x纳米片的质量比100：10(即实施例6)和100：50(即实施例7)时，复合水凝胶的最终光热平衡温度高于150℃，超过了热成像仪的检测范围。
以上结果表明，二维层状材料(具体为少层Ti 3C 2T x纳米片)的引入不仅显著提高了纤维素水凝胶的力学强度，而且确实能够赋予纤维素水凝胶优异的光热特性，而且这一特性可通过少层Ti 3C 2T x纳米片的含量进行调节。且当采用较低质量的少层Ti 3C 2T x纳米片时，就能使所述复合水凝胶达到较高的光热平衡温度。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (20)

  1. 一种纤维素/二维层状材料复合水凝胶，其特征在于，所述复合水凝胶包括纤维素三维网络结构、以及负载在所述纤维素三维网络结构中的二维材料，所述二维层状材料为二维过渡金属碳化物、氮化物或碳氮化物。
  2. 如权利要求1所述的复合水凝胶，其特征在于，所述二维层状材料的厚度为6-10nm；横向尺寸为60-200nm。
  3. 如权利要求1所述的复合水凝胶，其特征在于，所述纤维素三维网络结构包括纤维素或纤维素衍生物自身连接成的三维网络结构，或者纤维素和/或纤维素衍生物通过交联剂形成的三维网络结构。
  4. 如权利要求3所述的复合水凝胶，其特征在于，所述纤维素衍生物包括经氧化石墨烯、壳聚糖、环糊精和明胶中的至少一种所改性的纤维素，或羧基化、硅烷化的纤维素。
  5. 如权利要求3所述的复合水凝胶，其特征在于，所述交联剂包括环氧氯丙烷和异氰酸酯中的至少一种。
  6. 如权利要求1或3所述的复合水凝胶，其特征在于，所述纤维素三维网络结构具有孔径为40-130μm的孔隙结构。
  7. 如权利要求6所述的复合水凝胶，其特征在于，所述孔隙结构的孔径为50-80μm。
  8. 如权利要求1或3所述的复合水凝胶，其特征在于，所述纤维素三维网络结构中的纤维素与所述二维材料纳米片的质量比为100：(0.0001-50)。
  9. 如权利要求3所述的复合水凝胶，其特征在于，所述纤维素三维网络结构中的纤维素与交联剂的质量比为100：(1.372-13.71)。
  10. 一种纤维素/二维材料纳米片复合水凝胶的制备方法，其特征在于，包括以下步骤：
    (1)提供二维层状材料，所述二维层状材料为二维过渡金属碳化物、氮化物或碳氮化物；
    (2)配制含强碱、尿素和水的混合溶剂，并进行预冷，将纤维素粉末加入到预冷后的所述混合溶剂中，剧烈搅拌，得到纤维素溶液；
    (3)在高速搅拌条件下，将所述二维层状材料、交联剂与所述纤维素溶液相混合，超声处理后，于65-90℃下进行交联反应0.5-2小时，得到交联反应物；
    (4)向所述交联反应物中加入纤维素再生液浸泡30-60min，之后将再生后的交联反应物置于水中进行透析，得到纤维素/二维层状材料复合水凝胶。
  11. 如权利要求10所述的制备方法，其特征在于，所述混合溶剂中，强碱的质量浓度为5-15％，尿素的质量浓度为10-15％。
  12. 如权利要求10所述的制备方法，其特征在于，所述纤维素溶液中，混合溶剂与纤维素的质量比为100：(1-4)；所述纤维素溶液的质量与所述交联剂的质量比为100：(0.212-2.12)。
  13. 如权利要求10所述的制备方法，其特征在于，所述交联剂为带有环氧基和异腈酸酯基中的至少一种的不完全疏水物质。
  14. 如权利要求10所述的制备方法，其特征在于，所述纤维素粉末的粒径为10-30微米。
  15. 如权利要求10所述的制备方法，其特征在于，所述二维层状材料的化学式为M n+1X nT x，其中，M为过渡金属元素，X为碳元素和/或氮元素，n 为1-3的整数，T x表示表面基团，T可选自O 2-、OH -、F -和NH 4 +中的至少一种。
  16. 如权利要求10所述的制备方法，其特征在于，步骤(3)中，所述纤维素再生液为质量分数为5％-10％的稀硫酸溶液；所述交联反应物与所述稀硫酸溶液的体积比为1：(2-3)。
  17. 如权利要求10所述的制备方法，其特征在于，所述纤维素与黑磷纳米片的质量比为100：(0.0001-50)。
  18. 如权利要求17所述的制备方法，其特征在于，所述纤维素与黑磷纳米片的质量比为100：(0.0001-0.01)。
  19. 如权利要求10所述的制备方法，其特征在于，步骤(1)中，所述剧烈搅拌的转速为7000～10000rpm，所述剧烈搅拌的时间为1-3分钟；
    步骤(2)中，所述高速搅拌的转速为7000～10000rpm，所述高速搅拌的时间为1-3分钟。
  20. 如权利要求10所述的制备方法，其特征在于，纤维素/二维层状材料复合水凝胶，包括纤维素和交联剂交联成的纤维素三维网络结构，还包括负载在所述纤维素三维网络结构中的二维层状材料。
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