CN112175144A - Preparation method of multiple-response hydrogel based on compounding of natural polymer and synthetic polymer - Google Patents

Preparation method of multiple-response hydrogel based on compounding of natural polymer and synthetic polymer Download PDF

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CN112175144A
CN112175144A CN202011058732.8A CN202011058732A CN112175144A CN 112175144 A CN112175144 A CN 112175144A CN 202011058732 A CN202011058732 A CN 202011058732A CN 112175144 A CN112175144 A CN 112175144A
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朱申敏
陈天星
李尧
陶杰
沈洁清
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Shanghai Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K38/00—Medicinal preparations containing peptides
    • A61K38/04—Peptides having up to 20 amino acids in a fully defined sequence; Derivatives thereof
    • A61K38/14—Peptides containing saccharide radicals; Derivatives thereof, e.g. bleomycin, phleomycin, muramylpeptides or vancomycin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38—Cellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08K3/08—Metals
    • 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
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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

Abstract

The invention relates to a preparation method of a multiple-response hydrogel based on compounding of natural polymers and synthetic polymers, which comprises the following steps: (1) preparing a CNC solution from plant raw materials by using an acid hydrolysis method; (2) introducing metal ions with different valence states into the CNC solution, and synthesizing nano particles in situ under a certain condition to obtain a CNC-loaded nano particle colloidal solution; (3) and (3) adding a high-molecular monomer, an initiator, a cross-linking agent and a catalyst into the colloidal solution obtained in the step (2), and reacting to obtain the target product. Compared with the prior art, the preparation method disclosed by the invention has the advantages that the natural polymer CNC solution is used as a raw material, the in-situ growth of the nano particles with the photo-thermal conversion performance is taken as a basis, and the preparation of the multi-response hydrogel with better mechanical property can be realized by adding different contents and different types of polymers.

Description

Preparation method of multiple-response hydrogel based on compounding of natural polymer and synthetic polymer
Technical Field
The invention belongs to the technical field of gel materials, and relates to a preparation method of a multiple-response hydrogel based on compounding of natural polymers and synthetic polymers.
Background
With the continuous development of science and technology, people have more and more demands on hydrogel and have higher and more requirements on functions of the hydrogel. The temperature-responsive hydrogel can respond to external stimuli (temperature, pH, electric field, ion concentration and the like) to attract great attention, for example, the temperature-responsive hydrogel can undergo the transformation from liquid to gel along with the change of temperature, and the temperature-responsive hydrogel can be mixed with cells or medicaments, injected into tissues or injury sites in a liquid form and then transformed into gel to be used as a tissue engineering scaffold or a medicament controlled release carrier; pH-responsive hydrogels typically contain amino or carboxyl groups, which can impart variable solubility to the hydrogel, facilitating drug loading, controlled release, and targeted drug release. However, the single-responsive hydrogel is increasingly difficult to meet the requirements of special applications in fields such as drug controlled release and biosensors, and research and development of intelligent hydrogels capable of simultaneously responding to two or more external stimulus signals has become a hotspot of intelligent material research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a multiple-response hydrogel based on the compounding of natural polymers and synthetic polymers, and the preparation method is applied to controlled drug release. The preparation of the multi-response intelligent hydrogel is realized by taking the CNC solution loaded with the photothermal effect nano particles as a raw material and adding different contents and different types of response polymers, and the mechanical property of the hydrogel is greatly enhanced due to the existence of natural polymers.
The purpose of the invention can be realized by the following technical scheme: a preparation method of a multiple-response hydrogel based on compounding of natural polymers and synthetic polymers is characterized by comprising the following steps:
(1) preparing a CNC solution from plant raw materials by using an acid hydrolysis method;
(2) introducing metal ions with different valence states into the CNC solution, and synthesizing nano particles in situ under a certain condition to obtain a CNC-loaded nano particle colloidal solution;
(3) and (3) adding a high-molecular monomer, an initiator, a cross-linking agent and a catalyst into the colloidal solution obtained in the step (2), and reacting to obtain the target product.
In the step (1), the acid used for acid hydrolysis is sulfuric acid or hydrochloric acid, and the specific steps are as follows: adding plant raw materials into a mixed solution of strong acid and deionized water in a mass ratio of 1:1, heating to 65 ℃, hydrolyzing for 1-2h, adding deionized water for dilution, standing, centrifuging, dialyzing, and performing ultrasound to obtain a CNC solution.
The plant raw material is rich in cellulose and comprises one or more of cotton, hemp, filter paper, wood pulp, paper pulp, microcrystalline cellulose and bacterial cellulose. The plant material is added to the mixed solution in an amount to completely submerge the plant material in the mixed solution.
In the step (2), the introduced metal ions are Ag+，AuCl4 -，Fe3+One or more of the above-mentioned materials are respectively derived from AgNO3，HAuCl4·4H2O, and FeCl3·6H2And O. The method for in-situ synthesis, in which the mass ratio of the CNC to the metal nanoparticles in the CNC-loaded nanoparticle colloidal solution obtained by in-situ synthesis is 10-20: 1, comprises the following steps: mixing AgNO3，HAuCl4·4H2O, and FeCl3·6H2Adding one or more of O into the CNC solution, and reacting for 15min in ice water bath to obtain CNC loadA nanoparticle colloid solution.
In the step (3), the high molecular monomer comprises more than two of a pH response polymer monomer, a temperature-sensitive response polymer monomer and an ionic response polymer monomer; preferably, the mixture of the pH response polymer monomer and the temperature response polymer monomer is selected, wherein the adding mass ratio of one polymer monomer to the other polymer monomer is 1 (1-5). When two polymer monomers with the same type of response are added simultaneously, the mass ratio of the monomers is 1: 1.
The pH response polymer monomer is one or more of acrylic acid and/or methacrylic acid, dimethylaminoethyl methacrylate and polyvinyl pyridine;
the temperature-sensitive response polymer monomer is N-isopropyl acrylamide and/or N, N-diethyl acrylamide;
the ion response polymer monomer is homopolymerized polyacrylamide or copolymerized polyacrylamide.
In the step (3), the initiator is a free radical initiator, and is specifically selected from one or more of AIBN, BPO, potassium persulfate or ammonium persulfate;
the cross-linking agent is diene;
the catalyst is tetramethyl ethylene diamine.
The mass ratio of the high molecular monomer, the initiator, the cross-linking agent and the catalyst is 1 (0.01-0.02) to 0.01-0.08 to 0.005-0.01.
The mass ratio of the colloidal solution to the added high-molecular monomer in the step (3) is 1: 0.01-0.2.
And (3) adding a high molecular monomer into the colloidal solution in the step (3), and then carrying out ice-water bath ultrasound for 10-60min at the temperature of 0-5 ℃.
Compared with the prior art, the invention has the following advantages:
the CNC surface contains sulfonic group and is rich in hydroxyl, so that the CNC surface is easy to adsorb metal ions, and metal nano particles or metal oxide particles are generated on the CNC surface in situ under a certain condition after ammonia water or other reducing agents are added. Because of the high surface energy of the nanoparticles, agglomeration is very easy to occur. After the nano particles are loaded on the surface of the CNC, the agglomeration of the nano particles can be effectively prevented, the dispersity of the nano particles is enhanced, and the final photo-thermal conversion effect of the nano particles in the hydrogel is improved.
Hydroxyl groups on the CNC surface are also prone to hydrogen bonding with the temperature sensitive and pH responsive polymers. According to the invention, a water-soluble temperature-sensitive and pH-responsive polymer monomer is selected to be in a CNC nanoparticle colloidal solution, and the monomer polymerization is initiated at room temperature under the action of a catalyst to prepare the hydrogel, so that the common heating and oxygen removal process of polymerization is avoided. Meanwhile, due to the reinforcing effect of the natural polymer cellulose nanocrystals on the synthetic polymer, the obtained multi-response hydrogel has good mechanical property, and the tensile strength reaches 90-300 kPa.
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FIG. 1 is a scanning electron micrograph of a hydrogel obtained in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of the hydrogel obtained in example 2 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the mass ratio of the total amount of the polymer monomer to the amount of the crosslinking agent added was 1: 0.001. The carried medicine is vancomycin, the laser wavelength is 808nm, and the laser power density of the laser used during the release of the light-operated medicine is 2W/cm2。
The rest of the raw material products or treatment process technologies which are not particularly specified are conventional commercial products or conventional treatment technologies in the field.
Example 1:
step one, extracting a CNC solution from plant raw materials by using an acid hydrolysis method. The method specifically comprises the following steps: adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution.
Step two, taking the CNC solution (the mass fraction is 1.1wt percent), and adding AgNO3，AgNO3And NaBH4The mass ratio of the silver nanoparticles to the added silver nanoparticles is 1:5, the silver nanoparticles are synthesized in situ on the CNC (the mass ratio of the CNC to the generated silver nanoparticles is 11:1), and the mixture reacts for 15min in ice water bath to obtain a colloidal solution;
and step three, taking 5g of the colloidal solution obtained in the step two, adding 0.2g of high molecular monomer (0.1g N-isopropyl acrylamide, 0.1g of acrylic acid), carrying out ice-water bath ultrasound for 35min, sequentially adding 0.01g of initiator (potassium persulfate, the mass ratio of potassium persulfate to high molecular monomer is 0.01:1), 0.01g of cross-linking agent (N, N-methylene bisacrylamide, the mass ratio of potassium persulfate to high molecular monomer is 0.01:1) and 10 mu L of catalyst (tetramethyl ethylene diamine), stirring for 5min, and reacting for 24h to obtain the hydrogel.
Hydrogel concentration at 0.8W/cm2Under the irradiation of 808nm laser, the pH value of the buffer solution is 7, the temperature can be increased to more than 40 ℃ from room temperature within 4min, and the phase change condition of the poly N-isopropylacrylamide is completely met. The drug loading of the hydrogel was 3g/g of gel, where the gel was the dried hydrogel. The laser power density of the laser used during the optically controlled drug release is 2W/cm2The time taken for the drug release to reach maximum was 4.5 h.
Example 2
The specific method and procedure are mostly the same as in example 1, except that: in step three, 0.4g of a polymer monomer (0.2g N-isopropylacrylamide, 0.2g of acrylic acid) was added.
It can be seen from figures 1 and 2 that the polymer network entanglement density is significantly reduced when no cross-linking agent is added.
Example 3
The specific method and procedure are mostly the same as in example 1, except that: in step three, 0.6g of a polymer monomer (0.6g N-isopropylacrylamide, 0.3g of acrylic acid) was added.
Example 4
The specific method and procedure are mostly the same as in example 1, except that: in step three, 0.8g (0.4g N-isopropylacrylamide, 0.4g acrylic acid) of a polymer monomer was added
Example 5
The specific method and procedure are mostly the same as in example 1, except that: in step three, 1g of a polymer monomer (0.5g N-isopropylacrylamide, 0.5g of acrylic acid) was added.
The results are shown in Table 1.
TABLE 1
Figure BDA0002711665230000051
The tensile breaking strength and the tensile rate of the hydrogel are related to the contents of the cross-linking agent and the CNC silver nano particles, and the tensile breaking strength of the hydrogel added with the cross-linking agent is obviously higher than that of the hydrogel without the cross-linking agent, and the maximum tensile breaking strength reaches 270 kPa. Meanwhile, in comparison examples 1, 2, 3, 4 and 5, the relative content of the CNC silver nanoparticle composite material is increased, and the tensile strength of the hydrogel is increased from 92kPa to 270 kPa. However, the increase of the entanglement density of the molecular chains makes the slippage of the molecular chains more difficult, and the stretching ratio is reduced, and the stretching ratio of the hydrogel is reduced from 1000% to 400% in comparative examples 1 and 5. Meanwhile, when the relative content of the CNC silver nanoparticle composite material is increased, the photo-thermal conversion effect is more obvious, the infrared heating rate is higher, and in comparative examples 1 and 5, the hydrogel is at 0.8W/cm2Under the irradiation of 808nm laser, the infrared heating rate is increased from 7 ℃/min to 13 ℃/min. The drug loading of the hydrogel is related to the crosslinking density, and when the crosslinking agent is added, the hydrogel is more difficult to swell, and the drug loading is reduced. The maximum time for releasing the drug is related to the content of the CNC silver nanoparticle composite material, and compared with examples 1, 2, 3, 4 and 5, when the relative content of the silver particles is increased, the infrared heating rate of the hydrogel is increased, more light energy is converted into heat energy in unit time, so that the phase change degree of the temperature-sensitive polymer network is larger, the drug release efficiency is improved, and the time required for releasing the drug to the maximum is reduced from 8 hours to 3 hours.
Example 6
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer pH was 5.
Example 7
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer pH was 3.
Example 8
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer pH was 1.
Example 9
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer pH was 9.
Example 10
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer pH was 11.
Example 11
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer pH was 13.
TABLE 2
Figure BDA0002711665230000061
The rate of drug release is related to the pore size of the hydrogel network and the diffusion coefficient of the drug molecules. The size and shape of the pore diameter of the hydrogel can be adjusted according to different environmental changes such as temperature and pH, which has important significance for the application of the hydrogel as a drug sustained-release carrier. Under acidic conditions, the formation of hydrogen bonds inhibits the expansion of the hydrogel network, thereby reducing the release rate of the drug. In comparative examples 1, 6, 7 and 8, the acidity increased with decreasing pH, and-COO dissociated from polyacrylic acid molecules-Will be in contact with H+the-COOH group is combined with-CONH-in the poly-N-isopropylacrylamide network and adjacent-COOH to form hydrogen bonds, so that the expansion of the hydrogel network is inhibited, and the drug is released for the maximum time which is increased from 8h to 10.8 h. Under alkaline conditions, -COOH in polyacrylic acid molecules dissociates to form-COO-，-COO-In betweenThe electrostatic repulsion, and the reduced interaction with adjacent groups, eventually leads to a sufficient stretching of the gel molecular chains, an increase in the swelling degree and thus an increase in the release of the drug, and the release time of the drug to the maximum is reduced from 8 hours to 4 hours in comparative examples 1, 9, 10 and 11.
Example 12
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light is applied, and the temperature of the buffer solution is 20 ℃.
Example 13
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light was applied and the buffer was allowed to warm to 25 ℃.
Example 14
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light is applied, and the temperature of the buffer solution is 30 ℃.
Example 15
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light is applied, and the temperature of the buffer solution is 35 ℃.
Example 16
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light is applied, and the temperature of the buffer solution is 40 ℃.
Example 17
The specific method and procedure are mostly the same as in example 1, except that: in step three, no light is applied, and the temperature of the buffer solution is 45 ℃.
TABLE 3
Figure BDA0002711665230000071
The lowest eutectic temperature (LCST) of the poly-N-isopropylacrylamide is 32 ℃, when the temperature of the solution is lower than the LCST, the molecular chain of the poly-N-isopropylacrylamide presents hydrophilicity, water-soluble drug molecules are limited in a hydrogel molecular chain network, and when the temperature is higher than the LCST, the molecular chain of the poly-N-isopropylacrylamide presents hydrophobicity, presents volume phase change, shrinks, and releases the drug in the hydrogel. In comparative examples 12 to 17, when the temperature was gradually raised above the LCST, the higher the temperature, the more drastic the volume transition of poly-N-isopropylacrylamide was, and the time until the drug was released to the maximum was shortened, and more drug was released from the gel.
Example 18
Compared with example 1, most of them are the same except that in this example, the polymer monomer is added into the colloidal solution, and the ice bath ultrasound is performed for 10 min.
Example 19
Compared with example 1, most of the method is the same, except that in this example, the polymer monomer is added into the colloidal solution, and the ice bath ultrasound treatment is performed for 60 min.
Example 20
Compared with example 1, most of them are the same except that in this example, the mass ratio of the total amount of the polymer monomers, the initiator, the crosslinking agent and the catalyst is limited to 1:0.01:0.01: 0.005.
Example 21
Compared with example 1, the mass ratio of the total amount of the polymer monomers, the initiator, the crosslinking agent and the catalyst is 1:0.02:0.08: 0.01.
Example 22
Compared with example 1, the mass ratio of the total amount of the high molecular weight monomers, the initiator, the crosslinking agent and the catalyst is limited to 1:0.015:0.04: 0.007.
Example 23
Compared with example 1, the laser power is mostly the same except that in this example, the laser power is 1W/cm2。
Example 24
Compared with example 1, the laser power is mostly the same except that in this example, the laser power is 0.5W/cm2。
Example 25
Compared with example 1, the laser power is mostly the same except that in this example, the laser power is 1.5W/cm2。
Example 26
Compared with example 1, the laser power is mostly the same except that in this example, the laser power is 2.5W/cm2。
Example 27
Compared with example 1, the laser power is mostly the same except that in this example, the laser power is 3W/cm2。
Example 28
In comparison with the example 1, the method of the present invention,
in the step (1), the plant raw material is cotton, the amount of the plant raw material added into the mixed solution is that the plant raw material is completely immersed in the mixed solution, and the hydrolysis time is 1 h.
In the step (2), the introduced metal ions are AuCl4 -And the mass ratio of the CNC to the Au nano particles in the CNC-loaded nano particle colloidal solution obtained by in-situ synthesis is 10: 1.
The rest is the same as example 1.
Example 29
In comparison with the example 1, the method of the present invention,
in the step (1), the plant raw materials are a mixture of hemp, filter paper, wood pulp and paper pulp, the amount of the plant raw materials added into the mixed solution is that the plant raw materials are completely immersed in the mixed solution, and the hydrolysis time is 2 hours.
In the step (2), the introduced metal ions are Fe3+And the mass ratio of the CNC to the Fe nano particles in the CNC-loaded nano particle colloidal solution obtained by in-situ synthesis is 20: 1.
The rest is the same as example 1.
Example 30
In comparison with the example 1, the method of the present invention,
in the step (1), the plant raw material is a mixture of wood pulp, microcrystalline cellulose and bacterial cellulose.
In the step (2), the introduced metal ions are Ag+，AuCl4 -，Fe3+And the mass ratio of the CNC to the metal nanoparticles in the CNC-loaded nanoparticle colloidal solution obtained by in-situ synthesis is 15:1 (wherein the mass ratio of the Ag nanoparticles, the Au nanoparticles and the Fe nanoparticles is 1:1: 1).
The rest is the same as example 1.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of a multiple-response hydrogel based on compounding of natural polymers and synthetic polymers is characterized by comprising the following steps:
(1) preparing a CNC solution from plant raw materials by using an acid hydrolysis method;
(2) introducing metal ions with different valence states into the CNC solution, and synthesizing nano particles in situ under a certain condition to obtain a CNC-loaded nano particle colloidal solution;
(3) and (3) adding a high-molecular monomer, an initiator, a cross-linking agent and a catalyst into the colloidal solution obtained in the step (2), and reacting to obtain the target product.
2. The method for preparing the multiple-response hydrogel based on the combination of natural polymer and synthetic polymer according to claim 1, wherein the acid used for acid hydrolysis in step (1) is sulfuric acid or hydrochloric acid, and the method comprises the following steps: adding plant raw materials into a mixed solution of strong acid and deionized water in a mass ratio of 1:1, heating to 65 ℃, hydrolyzing for 1-2h, adding deionized water for dilution, standing, centrifuging, dialyzing, and performing ultrasound to obtain a CNC solution.
3. The method for preparing the multiple response hydrogel based on the composition of the natural polymer and the synthetic polymer according to claim 1 or 2, wherein the plant material is rich in cellulose, and comprises one or more of cotton, hemp, filter paper, wood pulp, paper pulp, microcrystalline cellulose and bacterial cellulose.
4. The method for preparing the multiple response hydrogel based on the combination of the natural polymer and the synthetic polymer according to claim 1, wherein the metal ions introduced in the step (2) are Ag+，AuCl4 -，Fe3+One or more of the above-mentioned materials are respectively derived from AgNO3，HAuCl4·4H2O, and FeCl3·6H2O。
5. The method for preparing the multiple-response hydrogel based on the combination of the natural polymer and the synthetic polymer according to claim 1, wherein in the step (3), the polymer monomers comprise two or more of pH-responsive polymer monomers, temperature-sensitive responsive polymer monomers and ion-responsive polymer monomers;
the pH response polymer monomer is one or more of acrylic acid and/or methacrylic acid, dimethylaminoethyl methacrylate and polyvinyl pyridine;
the temperature-sensitive response polymer monomer is N-isopropyl acrylamide and/or N, N-diethyl acrylamide;
the ion response polymer monomer is homopolymerized polyacrylamide or copolymerized polyacrylamide.
6. The method for preparing the multiple response hydrogel based on the combination of natural polymer and synthetic polymer according to claim 1, wherein in the step (3),
the initiator is a free radical initiator, and is specifically selected from one or more of AIBN, BPO, potassium persulfate or ammonium persulfate;
the cross-linking agent is diene;
the catalyst is tetramethyl ethylene diamine.
7. The method for preparing the multiple-response hydrogel based on the compounding of the natural polymer and the synthetic polymer according to claim 5, wherein the polymer monomer is a mixture of pH-responsive polymer monomers and temperature-responsive polymer monomers, and the adding mass ratio of one polymer monomer to the other polymer monomer is 1 (1-5).
8. The method for preparing the multiple-response hydrogel based on the composition of the natural polymer and the synthetic polymer according to claim 1, wherein the weight ratio of the polymer monomer, the initiator, the crosslinking agent and the catalyst is 1 (0.01-0.02): (0.01-0.08): 0.005-0.01).
9. The method for preparing the multiple-response hydrogel based on the compounding of the natural polymer and the synthetic polymer according to claim 1, wherein the mass ratio of the colloidal solution to the added polymer monomer in the step (3) is 1: 0.01-0.2.
10. The method for preparing the multiple-response hydrogel based on the compounding of the natural polymer and the synthetic polymer according to claim 1, wherein the polymer monomer is added into the colloidal solution in the step (3), and then the mixture is subjected to ice-water bath ultrasound at a temperature of 0-5 ℃ for 10-60 min.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104941610A (en) * 2015-06-09 2015-09-30 西安交通大学 Preparation and application of magnetic hydrogel loaded with one-dimensional Fe3O4 nanocrystals
US20160175812A1 (en) * 2014-12-22 2016-06-23 Nishil Mohammed PRISTINE AND SURFACE FUNCTIONALIZED CELLULOSE NANOCRYSTALS (CNCs) INCORPORATED HYDROGEL BEADS AND USES THEREOF
CN107722307A (en) * 2017-10-24 2018-02-23 湖北科技学院 A kind of magnetic, pH, temperature collaboration stimuli responsive hydrogel pre-irradiated synthetic method
CN109206666A (en) * 2018-04-27 2019-01-15 张金荣 A kind of nanocrystal cellulose aquagel and preparation method thereof
CN109666106A (en) * 2018-12-28 2019-04-23 河南省科学院能源研究所有限公司 A kind of hydrogel composite material and preparation method thereof with near-infrared response temperature sensitive properties
CN110903432A (en) * 2019-11-08 2020-03-24 上海交通大学 Preparation of photo-thermal response drug sustained-release hydrogel based on magnetic cellulose nanocrystal

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160175812A1 (en) * 2014-12-22 2016-06-23 Nishil Mohammed PRISTINE AND SURFACE FUNCTIONALIZED CELLULOSE NANOCRYSTALS (CNCs) INCORPORATED HYDROGEL BEADS AND USES THEREOF
CN104941610A (en) * 2015-06-09 2015-09-30 西安交通大学 Preparation and application of magnetic hydrogel loaded with one-dimensional Fe3O4 nanocrystals
CN107722307A (en) * 2017-10-24 2018-02-23 湖北科技学院 A kind of magnetic, pH, temperature collaboration stimuli responsive hydrogel pre-irradiated synthetic method
CN109206666A (en) * 2018-04-27 2019-01-15 张金荣 A kind of nanocrystal cellulose aquagel and preparation method thereof
CN109666106A (en) * 2018-12-28 2019-04-23 河南省科学院能源研究所有限公司 A kind of hydrogel composite material and preparation method thereof with near-infrared response temperature sensitive properties
CN110903432A (en) * 2019-11-08 2020-03-24 上海交通大学 Preparation of photo-thermal response drug sustained-release hydrogel based on magnetic cellulose nanocrystal

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ZIHE GUO，等: "Preparation of Photo-thermal Cellulose Nanocrystal-based Hydrogel", 《PBM》 *
徐步锋，等: "单分散银纳米颗粒的粒径调控及其光热转换性能", 《青岛科技大学学报》 *
杨燕兴，等: "温度/pH双重敏感性芦苇半纤维素基水凝胶的制备和表征", 《化工新型材料》 *
金征宇，等: "《基因如纳米探针-医学分子成像理论与实践》", 30 November 2017, 天津科学技术出版社 *

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