WO2019095752A1 - 一种纤维素/黑磷纳米片复合水凝胶及其制备方法 - Google Patents

一种纤维素/黑磷纳米片复合水凝胶及其制备方法 Download PDF

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WO2019095752A1
WO2019095752A1 PCT/CN2018/100241 CN2018100241W WO2019095752A1 WO 2019095752 A1 WO2019095752 A1 WO 2019095752A1 CN 2018100241 W CN2018100241 W CN 2018100241W WO 2019095752 A1 WO2019095752 A1 WO 2019095752A1
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cellulose
black phosphorus
composite hydrogel
phosphorus nanosheet
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
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/10—Crosslinking of cellulose
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • 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
    • C08K7/00—Use of ingredients characterised by shape

Definitions

  • the invention belongs to the field of preparation of black phosphorus-based nanomaterials, and particularly relates to a cellulose/black phosphorus nanosheet composite hydrogel and a preparation method thereof.
  • Black phosphorene is a new type of direct band gap two-dimensional material. Its band gap can be adjusted from 0.3eV (body state) to 1.5eV (single layer) through its number of layers, which can absorb visible light to communication infrared. Range wavelength light, combined with its high carrier mobility, high on-off ratio, and good photothermal conversion effect and biocompatibility, make it extremely large in the semiconductor field, optoelectronic field and biological field. Potential advantage.
  • the inorganic nanomaterial-black phosphorus has insufficient dispersibility in biological fluids and is prone to sedimentation, and its photothermal effect has obvious regional differences.
  • the structure of the black phosphorus-based material is too single, and the stability of black phosphorus in it is poor, and it is easy to be liberated, which cannot satisfy the targeting and durability required for the tumor treatment process. Therefore, it is necessary to expand the form of black phosphorus in the biomedical field.
  • 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/black phosphorus nanosheet composite hydrogel having high stability in the composite hydrogel, the cellulose/black phosphorus nanosheet composite hydrogel. It has good dispersibility in biological fluids, exhibits excellent characteristics of high photothermal conversion efficiency, complete biodegradability, complete biocompatibility, biosafety, etc., and has good mechanical strength, and is expected to be applied in biomedicine. In the field.
  • the present invention provides a cellulose/black phosphorus nanosheet composite hydrogel comprising a cellulose three-dimensional network structure, and black phosphorus nanoparticle supported on the cellulose three-dimensional network structure. sheet.
  • the black phosphorus nanosheet is wound by the three-dimensional network structure formed by the cellulose molecules.
  • black phosphorus nanosheets are loaded into the system to form a cellulose/black phosphorus nanosheet composite hydrogel.
  • the composite hydrogel significantly improves the dispersibility of the black phosphorus nanosheet and prevents agglomeration between the black phosphorus nanosheets.
  • the black phosphorus nanosheet has a thickness of 1-25 nm. More preferably, it is 3-18 nm.
  • a nano-thickness black phosphorus two-dimensional layered material can be more firmly loaded into the cellulose three-dimensional network structure.
  • the black phosphorus nanosheet has a layer number of from 1 to 20 layers, further preferably from 2 to 10 layers.
  • the black phosphorus nanosheet has a lateral dimension of from 100 to 800 nm.
  • the lateral dimension refers to the length or width of the black phosphorus nanosheet.
  • the cellulose three-dimensional network structure comprises a three-dimensional network structure in which cellulose or a cellulose derivative itself is joined, or a three-dimensional network structure in which cellulose and/or a cellulose derivative is formed by 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 30-300 ⁇ m.
  • the pore structure has a pore diameter of 50 to 280 ⁇ m. More preferably, it is 80-250 micrometer.
  • 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 the adhesion of the black phosphorus nanosheet to biological cells and tissues.
  • the mass ratio of the cellulose to the black phosphorus nanosheet in the cellulose three-dimensional network structure is 100: (0.0001-50), preferably 100: (0.001-10), further preferably 100: (0.001-5) More preferably, it is 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 cellulose/black phosphorus nanosheet composite hydrogel provided by the first aspect of the invention has a cellulose three-dimensional network structure as a carrier, and the black phosphorus nanosheet is stably loaded in the three-dimensional network structure, and the black phosphorus nanosheet is improved. Dispersion prevents the agglomeration between black phosphorus nanosheets and expands the product form of black phosphorus.
  • the cellulose/black phosphorus nanosheet composite hydrogel has good dispersibility in biological fluid, and exhibits excellent characteristics such as high photothermal conversion efficiency, complete biodegradability, complete biocompatibility, and biosafety. It has good mechanical strength and is expected to be used in the field of biomedicine, especially in the field of cancer treatment.
  • the present invention provides a method for preparing a cellulose/black phosphorus nanosheet composite hydrogel, comprising the following steps:
  • the cellulose/black phosphorus nanosheet composite hydrogel prepared by the above method comprises a cellulose three-dimensional network structure crosslinked by cellulose and a crosslinking agent, and further comprises black phosphorus supported in the cellulose three-dimensional network structure. Nanosheets. Further, the surface of the black phosphorus nanosheet 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 1-3 minutes.
  • 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 high-speed stirring rotation speed is 7000 to 10000 rpm, and the high-speed stirring time is 1-3 minutes.
  • the stirring speed and the stirring time of the vigorous stirring and the high-speed stirring may be the same or different.
  • the ultrasonic treatment has a power of 300-500 W and a time of 10-30 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 10-15 mL.
  • the cross-linking reactant is a hydrogel of cellulose/crosslinking agent/black phosphorus nanosheet/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: (1-4).
  • 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 black phosphorus nanosheet is 100: (0.0001-50).
  • 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), further preferably 100: (0.001 to 5), more preferably 100: 0.05.
  • the black phosphorus nanosheet 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 the cancer can be killed by regulating its content in the composite hydrogel.
  • the desired temperature of the cells such as 43-60 ° C
  • other common photothermal reagents such as nano gold, nano Pd, CuS and porphyrin, etc.
  • black phosphorus nanosheets can biodegrade in vivo. Its degradation products are safe phosphates, showing good biocompatibility and biosafety.
  • the mass ratio of the cellulose to the black phosphorus nanosheet 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 43.5-60° C., so that the composite hydrogel can have an irradiation power of 1.0/ Under the illumination of cm 2 of 808 nm laser, the photothermal equilibrium temperature reached 48-75 ° C. It can be seen that when the lower quality black phosphorus nanosheet is contained, the composite hydrogel can be given a good photothermal effect of killing tumor cells.
  • the black phosphorus nanosheet has a thickness of 1-25 nm. More preferably, it is 3-18 nm.
  • the black phosphorus nanosheet has a layer number of from 1 to 20 layers, further preferably from 2 to 10 layers.
  • the black phosphorus nanosheet has a lateral dimension of from 100 to 800 nm.
  • the lateral dimension refers to the length or width of the black phosphorus nanosheet.
  • the preparation method of the black phosphorus nanosheet is not limited, and may be prepared in the following manner:
  • Grown black phosphorus and an organic solvent are mixed and ground, and the organic solvent is added to the mixture obtained by grinding to obtain a dispersion; the dispersion is subjected to probe-type ultrasonic for 30-60 hours at a power of 1000 to 1400 W.
  • the solution obtained after the ultrasonication was subjected to low-speed centrifugation, the supernatant was collected, and the supernatant was centrifuged at a high speed, and a solid precipitate was collected, and the solid precipitate was vacuum dried to obtain the black phosphorus nanosheet.
  • the ratio of the mass of the black phosphorus 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 black phosphorus, and there is a certain interaction between the two to balance the energy required to peel off the bulk black phosphorus.
  • 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/black phosphorus nanosheet composite hydrogel provided by the invention is as follows: 1) Firstly, the cellulose chain is dissolved by using a low temperature alkaline mixed solvent of sodium hydroxide, urea and water to dissolve the cellulose. The hydrogen bond network is gradually opened to form the sodium and hydroxide ions of the hydrate, forming a new hydrogen bond network with the molecular chain of cellulose, and the urea molecular hydrate prevents the self-ligation of the cellulose molecular chain.
  • the final 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 common solvents including aqueous solvents.
  • the alkaline solution also helps to improve the stability of the black phosphorus nanosheet and protect it from oxidation. 2)
  • the cellulose aqueous solution is mixed with the black phosphorus nanosheet and the crosslinking agent under high-speed stirring, after ultrasonication, the cellulose molecular chain and the crosslinking agent undergo nucleophilic reaction at a certain temperature, and the black phosphorus nanosheet is chiseled at the same time.
  • the black phosphorus nanosheets are placed in an extremely stable state to form a three-dimensional network of cellulose/crosslinking agent/black phosphorus nanosheet/sodium hydroxide/urea hydrogel.
  • the cellulose/crosslinking agent/black phosphorus nanosheet/sodium hydroxide/urea hydrogel is regenerated after being immersed in a dilute sulfuric acid solution, that is, the cellulose molecular chain is precipitated and appears to be convenient.
  • the regenerated hydrogel is taken out, and after soaking in water, sodium hydroxide and urea can be removed to finally obtain a cellulose/black phosphorus nanosheet composite hydrogel.
  • the black phosphorus nanosheet is stably supported in a three-dimensional network structure in which cellulose and a crosslinking agent are crosslinked, and the black phosphorus nanometer is blocked by the cellulose macromolecular chain.
  • the sheet 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, is easily dispersed in an aqueous solution or a biological body fluid, and has excellent compatibility with body fluids, which can improve the adhesion of the black phosphorus nanosheet to biological cells and tissues. Attached.
  • 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 is also fully biodegradable, fully biocompatible, biosafe, etc. Excellent characteristics.
  • the preparation method of the cellulose/black phosphorus nanosheet composite hydrogel provided by the second aspect of the invention has the advantages of simple process, green environmental protection, excellent performance and stable uniformity of the obtained product.
  • TEM transmission electron microscope
  • AFM atomic force microscope
  • Figure 3 is a macroscopic photograph of a cellulose hydrogel (Comparative Example 4) and a cellulose/black phosphorus nanosheet composite hydrogel (Example 4).
  • Example 4 is a scanning electron microscope (SEM) photograph of an aerogel obtained by freeze-drying a cellulose/black phosphorus nanosheet composite hydrogel according to Example 4 of the present invention; wherein (b) is an enlargement of a region in (a).
  • SEM scanning electron microscope
  • Step (1) Preparing a uniform size black phosphorus nanosheet solid by liquid phase stripping method, the specific steps are as follows:
  • the obtained black phosphorus nanosheets were tested to have a lateral dimension of 200-400 nm, a number of layers of 15 layers, and a thickness of 9 nm.
  • Step (2) Preparing an alkaline aqueous solution of transparent and uniform cellulose, the specific steps of which are as follows:
  • Step (3) Preparing a composite hydrogel of cellulose/black phosphorus nanosheet, the specific steps are as follows:
  • the composite hydrogel of the cellulose/black phosphorus nanosheet prepared in Example 1 of the present invention comprises a three-dimensional network structure in which cellulose molecules and a crosslinking agent are crosslinked, and a black phosphorus nanosheet supported in the three-dimensional network structure. .
  • the composite hydrogel of the cellulose/black phosphorus nanosheet was prepared, and the difference from Example 1 was that in the step 3-a), the mass ratio of the cellulose to the black phosphorus nanosheet solid was 100:0.01.
  • the composite hydrogel for preparing a cellulose/black phosphorus nanosheet differs from Example 1 in that the mass ratio of cellulose to black phosphorus nanosheet solids in step 3-a) is 100:0.03.
  • a composite hydrogel for preparing a cellulose/black phosphorus nanosheet differs from Example 1 in that the mass ratio of cellulose to black phosphorus nanosheet solids in step 3-a) is 100:0.05.
  • a composite hydrogel for preparing a cellulose/black phosphorus nanosheet differs from Example 1 in that the mass ratio of cellulose to black phosphorus nanosheet solids in step 3-a) is 100:5.
  • a composite hydrogel for preparing a cellulose/black phosphorus nanosheet differs from Example 1 in that the mass ratio of cellulose to black phosphorus nanosheet solids in step 3-a) is 100:10.
  • the composite hydrogel for preparing a cellulose/black phosphorus nanosheet differs from Example 1 in that the mass ratio of cellulose to black phosphorus nanosheet solids in step 3-a) is 100:50.
  • the present invention also provides the following comparative examples:
  • 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 100:0.4.
  • 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 volume ratio of the cellulose solution to the epichlorohydrin was 100:0.6.
  • 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 100:1.0.
  • 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 100:1.4.
  • 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 ratio of the volume of the cellulose solution to the epichlorohydrin was 100:2.0.
  • FIG. 1 is a transmission electron microscope micromorphology diagram of a black phosphorus nanosheet 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 black phosphorus nanosheets was tested as follows: Instrumentation: High resolution transmission electron microscope; Model: FEI Tecnai G 2 F30; Test high pressure: 300 kV.
  • the black phosphorus nanosheet has a size of about 100 nm ⁇ 400 nm; as shown in (b) of FIG. 1, the black phosphorus nanosheet shows a distinct lattice fringe, indicating black in the present invention.
  • the phosphorus nanosheet has a good crystal structure; its lattice size is 0.223 nm, which corresponds to the (014) diffractive surface.
  • FIG. 2 is an atomic force microscope photograph of a black phosphorus nanosheet used in the present invention.
  • the test conditions of the height map of the black phosphorus nanosheet are as follows: Instrumentation: High resolution atomic force microscope; Model: Brooke scanning probe microscope; Scan mode: Intelligent scanning mode.
  • the thickness of these black phosphorus nanosheets is in the range of 1.4 to 25 nm.
  • Figure 3 provides a macroscopic photograph of a cellulose hydrogel (Comparative Example 4) and a cellulose/black phosphorus nanosheet (Example 4). It can be seen from Fig. 3 that the pure cellulose hydrogel (Comparative Example 4) has a colorless and translucent "jelly-type" macroscopic morphology as a whole; and after the black phosphorus nanosheet is successfully introduced, the obtained cellulose/black phosphorus nanosheet is obtained.
  • the composite hydrogel (Example 4) was entirely brown in color with a sharp contrast of colors.
  • test conditions are as follows:
  • the tested hydrogel (the cellulose hydrogel of Comparative Example 4 and the cellulose/black phosphorus nanosheet composite hydrogel of Example 4) was first freeze-dried.
  • the corresponding aerogel structure was obtained, wherein the experimental conditions of freeze-drying were: temperature: -80 ° C; time: 72 hours.
  • the micromorphology was tested, and the instrument equipment used was: cold field emission scanning electron microscope; model: SEM-Hitachi SU8010; test voltage: 3 kV; silver plating time of sample surface: 20 seconds.
  • both types of aerogels exhibit significant porosity, which is determined by the three-dimensional gel network structure of cellulose.
  • the aerogel corresponding to the composite hydrogel of the cellulose/black phosphorus nanosheet prepared by the invention has a relatively uniform pore structure, a pore diameter of 80-280 ⁇ m and a porosity of about 85%.
  • Table 1 shows typical compositions and physical properties of Comparative Examples 1-6 and Examples 1-7 of the present invention.
  • Table 1 shows typical compositions and physical properties of Comparative Examples 1-6 and Examples 1-7 of the present invention.
  • 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.
  • the final photothermal equilibrium temperature of the composite hydrogel can reach 43.5 ° C and 49.7 at 0.5 and 1.0 W/cm 2 , respectively. °C, about 18.5 ° C and 24.7 ° C, respectively, compared to pure cellulose hydrogel.
  • this photothermal equilibrium temperature greatly increases or exceeds the detection range of the thermal imager.
  • the mass ratio of cellulose to black phosphorus nanosheet is 100:5 (ie, Example 5)
  • the final photothermal equilibrium temperature of the composite hydrogel is 110 and 130.4 ° C at 0.5 and 1.0 W/cm 2 , respectively;
  • the mass ratio of cellulose to black phosphorus nanosheet is 100:10 (ie, Example 6) and 100:50 (ie, Example 7)
  • the final photothermal equilibrium temperature of the composite hydrogel is higher than 150 ° C, exceeding the thermal imager. The scope of detection.

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Abstract

提供了一种纤维素/黑磷纳米片复合水凝胶及其制备方法，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黑磷纳米片。黑磷纳米片可被稳定地负载在该复合水凝胶体系中，不易团聚，所述复合水凝胶具有均匀、稳定的高光热转换效率，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。

Description

一种纤维素/黑磷纳米片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201711129778.2、发明名称为“一种纤维素/黑磷纳米片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
本发明属于黑磷基纳米材料制备领域，具体涉及一种纤维素/黑磷纳米片复合水凝胶及其制备方法。
背景技术
黑磷(Black phosphorene)是一种新型直接带隙二维材料，其带隙可从0.3eV(本体状态)到1.5eV(单层)通过其层数进行调节，可以吸收从可见光到通讯用红外线范围波长的光，加之其较高的载流子迁移率、高通断比，以及良好的光热转换效应和生物相容性，使得其在半导体领域、光电领域以及生物领域等显示出极大的潜在优势。
在生物医学领域中，无机纳米材料-黑磷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。而且目前黑磷基材料的结构过于单一，且黑磷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，有必要拓展黑磷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/黑磷纳米片复合水凝胶，黑磷纳米片在该复合水凝胶中的稳定性较高，所述纤维素/黑磷纳米片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、完全生物可降解性、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/黑磷纳米片复合水凝胶，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上的黑磷纳米片。
由于黑磷纳米片之间相互作用较弱，无法通过自组装行为来搭建纯黑磷纳米片的凝胶，本发明中主要借助纤维素分子形成的三维网络结构，将黑磷纳米片缠绕到该纤维素三维网络结构中，使黑磷纳米片负载到该体系中，形成纤维素/黑磷纳米片复合水凝胶。其中，所述复合水凝胶显著提高了黑磷纳米片的分散性，阻止了黑磷纳米片之间的团聚。
优选地，所述黑磷纳米片的厚度为1-25nm。进一步优选为3-18nm。纳米级厚度的黑磷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。
优选地，所述黑磷纳米片的层数为1-20层，进一步优选为2-10层。
优选地，所述黑磷纳米片的横向尺寸为100-800nm。所述横向尺寸是指黑磷纳米片的长度或宽度。
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30-300μm的孔隙结构。优选地，所述孔隙结构的孔径为50-280μm。进一步优选为80-250μm。
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，这可提高所述黑磷纳米片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黑磷纳米片的质量比为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/黑磷纳米片复合水凝胶，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黑磷纳米片，提高了黑磷纳 米片的分散性，阻止了黑磷纳米片之间的团聚，拓展了黑磷的产品形式。所述纤维素/黑磷纳米片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、完全生物可降解性、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/黑磷纳米片复合水凝胶的制备方法，包括以下步骤：
(1)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；
(2)在高速搅拌条件下，将黑磷纳米片、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；
(3)向所述交联反应物中加入纤维素再生液进行浸泡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/黑磷纳米片复合水凝胶。
采用上述方法制得的纤维素/黑磷纳米片复合水凝胶，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黑磷纳米片。进一步地，所述黑磷纳米片表面被所述纤维素三维网络结构所覆盖。
其中，步骤(1)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(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(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。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。
其中，步骤(2)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(2)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(3)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/黑磷纳米片/氢氧化钠/尿素的水凝胶。
其中，步骤(3)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(1)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(1)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，所述纤维素与黑磷纳米片的质量比为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。
所述黑磷纳米片可在近红外光(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，黑磷纳米片可在生物体内发生生物降解行为，其降解产物为安全性的磷酸盐，表现出了较好的生物相容性和生物安全性。
可选地，所述纤维素与黑磷纳米片的质量比为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43.5-60℃，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48-75℃。可见，含有较低质量的黑磷纳米片时，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。
优选地，所述黑磷纳米片的厚度为1-25nm。进一步优选为3-18nm。
优选地，所述黑磷纳米片的层数为1-20层，进一步优选为2-10层。
优选地，所述黑磷纳米片的横向尺寸为100-800nm。所述横向尺寸是指黑磷纳米片的长度或宽度。
本发明中，所述黑磷纳米片的制备方式不限，可以是采用如下方式制备得到：
将块状黑磷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，得到所述黑磷纳米片。
可选地，所述黑磷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黑磷的表面能相匹配，二者之间存在一定的相互作用平衡了剥离该块状黑磷所需要的能量。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/黑磷纳米片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黑磷纳米片的稳定性、保护黑磷以防其被氧化。2)当将纤维素水溶液与黑磷纳米片、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，同时将黑磷纳米片嵌合进来，使黑磷纳米片处于极为稳定的状态，形成三维网状结构的纤维素/交联剂/黑磷纳米片/氢氧化钠/尿素的水凝胶。3)所述纤维素/交联剂/黑磷纳米片/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/黑磷纳米片复合水凝胶。
所述纤维素/黑磷纳米片复合水凝胶中，黑磷纳米片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，黑磷纳米片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，这可提高所述黑磷纳米片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、黑磷纳米片均为可降解、生物相容性好的材料，使所述复合水凝胶也具有完全生物可降解性、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/黑磷纳米片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黑磷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10nm)。
图2为本发明实施例中采用的黑磷纳米片的原子力显微镜(AFM)照片，包括AFM高度图(左侧)以及相应的三个不同尺寸黑磷纳米片的厚度(右侧)。
图3为纤维素水凝胶(对比例4)和纤维素/黑磷纳米片复合水凝胶(实施例4)的宏观实物照片。
图4为本发明实施例4中纤维素/黑磷纳米片复合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；其中(b)为(a)中区域的放大。
图5为对比例4中纤维素水凝胶经冷冻干燥后所得气凝胶的SEM照片；其中(b)为(a)中区域的放大。
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，本发明实施例所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/黑磷纳米片复合水凝胶的制备，包括：
步骤(1).通过液相剥离法制备出尺寸均一的黑磷纳米片固体，其具体步骤如下：
1-a):将块状黑磷和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；研磨后将黑磷/N-甲基吡咯烷酮(NMP)的复合物移至100mL反应瓶中，并加入90mL的NMP，得到分散液，最终黑磷在总的NMP中的固含量为5mg/mL。
1-b):将上述分散液进行探针超声，超声功率为600W，时间为50小时，得到含黑磷纳米片的溶液，待用。
1-c):对上述黑磷纳米片溶液进行低速离心，转速为7000rpm，时间为25分钟，缓慢取出3/4的上清液。
1-d):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，收集黑磷纳米片固体。
1-e):将上述黑磷纳米片固体在真空干燥箱里干燥20小时，温度为75℃，最终得到干燥的黑磷纳米片固体，待用。
经测试，所得黑磷纳米片的横向尺寸为200-400nm，层数为15层，厚度为9nm。
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/黑磷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)中的黑磷纳米片固体，其中纤维素与黑磷纳米片固体的质量比为100：0.0001，取环氧氯丙烷0.05mL，即纤维素溶液与环氧氯丙烷的体积之比为100：1；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/黑磷纳米片/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/黑磷纳米片/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/黑磷纳米片的复合水凝胶。
本发明实施例1制得的纤维素/黑磷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黑磷纳米片。
实施例2
制备纤维素/黑磷纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与黑磷纳米片固体的质量比为100：0.01。
实施例3
制备纤维素/黑磷纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与黑磷纳米片固体的质量比为100：0.03。
实施例4
制备纤维素/黑磷纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与黑磷纳米片固体的质量比为100：0.05。
实施例5
制备纤维素/黑磷纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与黑磷纳米片固体的质量比为100：5。
实施例6
制备纤维素/黑磷纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与黑磷纳米片固体的质量比为100：10。
实施例7
制备纤维素/黑磷纳米片的复合水凝胶，与实施例1的区别在于，步骤3-a)中，纤维素与黑磷纳米片固体的质量比为100：50。
为突出本发明的有益效果，本发明还提供了以下对比实施例：
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0.01mL，即纤维素溶液与环氧氯丙烷的体积之比为100：0.2；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100：0.4。
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100：0.6。
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100：1.0。
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100：1.4。
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100：2.0。
图1为本发明实施例中所使用的黑磷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。
黑磷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，黑磷纳米片的尺寸约100纳米×400纳米；由图1中(b)可知，黑磷纳米片显示出了明显的晶格条纹，表明本发明中的黑磷纳米片具有较好的晶体结构；其晶格尺寸为0.223纳米，对应于(014)衍射面。
图2为本发明中所使用的黑磷纳米片的原子力显微镜照片。黑磷纳米片的高度图的测试条件如下：仪器设备：高分辨原子力显微镜；型号：布鲁克扫描探针显微镜；扫描模式：智能扫描模式。
由图2可知，这些黑磷纳米片的厚度在1.4-25nm的分布范围内。
图3提供了纤维素水凝胶(对比例4)和纤维素/黑磷纳米片(实施例4)的宏观实物照片。由图3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；而在黑磷纳米片成功引入后，所得纤维素/黑磷纳米片的复合水凝胶(实施例4)整体呈咖啡色，二者具有鲜明的颜色对比。
图4和图5分别提供了纤维素/黑磷纳米片复合水凝胶(实施例4)和纤维素水凝胶(对比例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/黑磷纳米片复合水凝胶)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为：温度：-80℃；时间：72小时。然后进行微观形貌的测试，采用的仪器设备为：冷场发射扫描电子显微镜；型号：SEM-Hitachi SU8010；测试电压：3kV；样品表面镀银时间：20秒。
由图4和图5的对比可知，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/黑磷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80-280μm，气孔率约为85％。
将对比例1-6制得的纤维素水凝胶与实施例1-7所制备的纤维素/黑磷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 PCTCN2018100241-appb-000001
Figure PCTCN2018100241-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(即对比例4)和100：2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即纤维素/环氧氯丙烷/黑磷纳米片的复合水凝胶中，由于黑磷纳米片的引入，其最终的光热平衡温度大幅度升高。例如，当纤维素与黑磷纳米片的质量比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43.5℃和49.7℃，与纯纤维素水凝胶相比，约分别提高了18.5℃和24.7℃。当继续增大纤维素/环氧氯丙烷/黑磷纳米片的复合水凝胶中黑磷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，当纤维素与黑磷纳米片的质量比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110和130.4℃；当纤维素与黑磷纳米片的质量比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，黑磷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黑磷纳米片的含量进行调节。且当采用较低质量的黑磷纳米片时，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/黑磷纳米片复合水凝胶，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黑磷纳米片。
  2. 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。
  3. 如权利要求2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。
  4. 如权利要求2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。
  5. 如权利要求1或2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30-300μm的孔隙结构。
  6. 如权利要求5所述的复合水凝胶，其特征在于，所述孔隙结构的孔径为50-280μm。
  7. 如权利要求1或2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黑磷纳米片的质量比为100：(0.0001-50)。
  8. 如权利要求2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)。
  9. 一种纤维素/交联剂/黑磷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)配制含强碱、尿素和水的混合溶剂，并将其预冷至-15～-5℃，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；
    (2)在高速搅拌条件下，将黑磷纳米片、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；
    (3)向所述交联反应物中加入纤维素再生液进行浸泡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/黑磷纳米片复合水凝胶。
  10. 如权利要求9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％。
  11. 如权利要求9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)。
  12. 如权利要求9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。
  13. 如权利要求9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。
  14. 如权利要求9所述的制备方法，其特征在于，所述黑磷纳米片的横向尺寸为100-800nm，所述黑磷纳米片的厚度为1-25nm。
  15. 如权利要求9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)。
  16. 如权利要求9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)。
  17. 如权利要求16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)。
  18. 如权利要求9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。
  19. 如权利要求9所述的制备方法，其特征在于，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。
  20. 如权利要求9所述的制备方法，其特征在于，所述纤维素/黑磷纳米片复合水凝胶，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黑磷纳米片。
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CN112341638B (zh) * 2020-11-05 2022-07-15 云南师范大学 一种多孔结构水凝胶材料及其制备与应用
CN112341638A (zh) * 2020-11-05 2021-02-09 云南师范大学 一种多孔结构水凝胶材料及其制备与应用
CN112851975A (zh) * 2021-01-12 2021-05-28 河北工程大学 一种基于Fe3O4纳米片交联结构聚丙烯酰胺水凝胶的制备方法
CN112851975B (zh) * 2021-01-12 2022-04-01 河北工程大学 一种基于Fe3O4纳米片交联结构聚丙烯酰胺水凝胶的制备方法
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CN113943444A (zh) * 2021-10-21 2022-01-18 桂林理工大学 一种多级孔隙结构的气-水凝胶的制备方法及其产品
CN113943444B (zh) * 2021-10-21 2022-12-27 桂林理工大学 一种多级孔隙结构的气-水凝胶的制备方法及其产品
CN113925999A (zh) * 2021-10-29 2022-01-14 华中科技大学 一种硅磷基复合支架及其制备方法和应用
CN114381343A (zh) * 2022-01-27 2022-04-22 鲁西工业装备有限公司 一种超声波除垢添加剂及其除垢方法
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