CN116496550B - Polymer capable of generating high-bionic intelligent hydrogel, double-network intelligent hydrogel, and preparation method and application thereof - Google Patents
Polymer capable of generating high-bionic intelligent hydrogel, double-network intelligent hydrogel, and preparation method and application thereof Download PDFInfo
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- CN116496550B CN116496550B CN202211670050.1A CN202211670050A CN116496550B CN 116496550 B CN116496550 B CN 116496550B CN 202211670050 A CN202211670050 A CN 202211670050A CN 116496550 B CN116496550 B CN 116496550B
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- hydrogel
- carbomer
- polyurethane
- biological
- carboxymethyl chitosan
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
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- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention belongs to the field of polymers, and discloses a polymer capable of generating high-bionic intelligent hydrogel, which comprises degradable biological polyurethane, wherein the biological polyurethane is subjected to crosslinking treatment by carboxymethyl chitosan and carbomer; wherein the biological polyurethane and carboxymethyl chitosan are subjected to chemical crosslinking, and the biological polyurethane and carboxymethyl chitosan are subjected to surface crosslinking with carbomer through hydrogen bonds and ionic bonds. The polymer is dispersed in water to form a hydrogel, which is a smart hydrogel having ductility, ionic conductivity, rapid stimulus responsiveness, degradability, and 3D/4D printability. Meanwhile, the invention also provides a double-network intelligent hydrogel and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the field of polymers, and particularly relates to a polymer capable of generating high-bionic intelligent hydrogel, a dual-network intelligent hydrogel, and a preparation method and application thereof.
Background
One key function of smart hydrogels is sensing. Unlike the electronic sensing of conventional hydrogels, the human tactile sensation is derived from the generation of bio-ionic currents on the skin surface upon mechanical stimulation, which are transmitted via nerves to the brain, thereby sensing. Smart hydrogels mimicking the human sensing mechanism need to have a continuous pore structure that provides channels for ion movement. Therefore, when the intelligent hydrogel is subjected to mechanical stimulation, the mechanical stimulation can be converted into an ion signal to be transmitted to a computer. At the same time, another key function of smart hydrogels is autonomous actuation. The intelligent hydrogel with the autonomous driving function can autonomously change shape or function under physical or chemical stimulation. In order to achieve the autonomous driving effect, the smart hydrogel needs to have the following three conditions. First, hydrogels consist of non-uniform stimuli-responsive and non-stimuli-responsive components. Second, a strong interfacial bond is required between the different components. Finally, the shaped hydrogels need to have controlled stress in the stimulus response. The stimulus response internal stress of the material can be accurately controlled by using a 3D printing technology, and the intelligent hydrogel model with controllable stimulus response internal stress is prepared.
The intelligent hydrogel with two functions of sensing and autonomous driving can realize the highly bionic action of automatically grabbing the object after sensing the object like a human hand. This will greatly advance the development of the field of flexible electronic devices such as fully soft robots. However, the application of smart hydrogels is severely limited by the following: 1) The main properties of hydrogels, such as mechanical properties, response properties and electrical conductivity, are mutually contradictory. Thinner hydrogels have faster response speeds, but tend to have poorer mechanical and electrical properties; 2) The hydrogel can be dried rapidly outdoors, so that the performances such as flexibility, conductivity and the like of the hydrogel are reduced; 3) With the conventional molding method, the hydrogel is difficult to make a shape and a structure with high precision, so there is little opportunity to improve the overall performance of the hydrogel electronic device from the standpoint of structural design; 4) The environmental burden is exacerbated by the large amount of low-degradability hydrogel electronic waste. These limitations make smart hydrogels difficult to apply as the primary sensitive material in flexible biomimetic electronics.
CN113290844a discloses a multistage suspension printing method for constructing complex heterogeneous tissues/organs. The method comprises the following steps: s1, preparing biological ink, wherein the biological ink is formed by crosslinked cell-carrying gel microspheres or is obtained by mixing the crosslinked cell-carrying gel microspheres with one or more uncrosslinked gel materials; s2, printing biological ink in a suspension medium to construct a specific tissue/organ structure; s3, further performing secondary or multistage substructure printing inside the tissue/organ structure obtained in the S2; s4, after printing, dissolving out the suspension medium after integral crosslinking. The multistage suspension 3D printing method is based on gel microsphere ink with the characteristics of shear thinning and self-healing, can be used for printing and forming in a suspension medium, can be used as a suspension medium for printing of a next-stage structure, is suitable for constructing a tissue organ model with a vascular channel and a heterogeneous cell structure, and is beneficial to promoting clinical application of engineering tissues/organs in regeneration and repair treatment.
The description is as follows: in the step S1 of the above method, the gel used by the cell-carrying gel microsphere and the gel material may be natural polymer hydrogel and/or synthetic polymer hydrogel; the natural polymer hydrogel material can be at least one of sodium alginate, gelatin, collagen, matrigel, chitosan, silk fibroin, hyaluronic acid, fibrinogen, chondroitin sulfate, albumin and their methacryloyl products (such as methacryloyl gelatin (GelMA), methacryloyl sodium alginate (AlgMA), etc.); the supermolecule self-healing hydrogel can be at least one of cyclodextrin-based supermolecule hydrogel, DNA supermolecule hydrogel, polyurethane urea supermolecule hydrogel, hyaluronic acid-glucan supermolecule hydrogel, tanshinone II-A polypeptide supermolecule hydrogel and graphene composite supermolecule hydrogel;
it can be seen that in the prior art, most of the smart hydrogels are suggested by models of tissue materials and do not involve the realization of stimulus responses.
Therefore, the technical problem solved by the scheme is as follows: how to develop a smart hydrogel and polymers related to the hydrogel that can be synergistic in mechanical, responsive and conductive properties.
Disclosure of Invention
The invention mainly aims to provide a polymer capable of generating high-bionic intelligent hydrogel, which is dispersed in water to form hydrogel, wherein the hydrogel is intelligent hydrogel with ductility, ionic conductivity, rapid stimulus response, degradability and 3D/4D printing suitability.
Meanwhile, the invention also provides a double-network intelligent hydrogel and a preparation method and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a polymer capable of generating high bionic intelligent hydrogel comprises degradable biological polyurethane, wherein the biological polyurethane is subjected to crosslinking treatment by carboxymethyl chitosan and carbomer; wherein the biological polyurethane and carboxymethyl chitosan are chemically crosslinked, and the biological polyurethane and the carboxymethyl chitosan are subjected to surface crosslinking through hydrogen bonds; the high bionic intelligent hydraulic condenser with sensing and actuating capabilities is obtained.
In the polymer, the biological polyurethane consists of a soft segment unit and a hard segment unit; the soft segment unit is one or more of polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid; the hard segment unit is isophorone diisocyanate; the mole ratio of the soft segment raw material to the hard segment raw material is 1:1 to 3.
It should be noted that, the soft segment unit of the present invention may also select other polyols, and the above three are preferably selected, so that the effect is optimal; alternative polyols include, but are not limited to:
the polyol may be selected from one or more short chain di-or tri-alcohols of 2 to 20, or 2 to 12, or 2 to 10 or 2 to 8 carbon atoms, specific examples include lower aliphatic polyols and short chain aromatic diols having a molecular weight of less than 500 or less than 300. Such as alkanediols, cycloaliphatic diols, alkylaryl diols, etc. Exemplary alkanediols include ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-Butanediol (BDO), 1, 3-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, dipropylene glycol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, tripropylene glycol, triethylene glycol and 3-methyl-1, 5-pentanediol. Examples of suitable cycloaliphatic diols include 1, 2-cyclopentanediol and 1, 4-Cyclohexanedimethanol (CHDM). Examples of suitable aryl and alkylaryl diols include hydroquinone bis (beta-hydroxyethyl) ether (HQEE), 1, 2-dihydroxybenzene, 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, 1,2, 3-trihydroxybenzene, 1,2- (hydroxymethyl) benzene, 1, 4-bis (hydroxymethyl) benzene, 1, 3-bis (2-hydroxyethyl) benzene, 1, 2-bis (2-hydroxyethoxy) benzene, 1, 4-bis (2-hydroxyethoxy) benzene, bis-ethoxybiphenol, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol a), bisphenol a ethoxylates, bisphenol F ethoxylates, 4-isopropylidenediphenol, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane (HEPP), mixtures thereof, and the like.
The hard segment units of the present invention are most preferably isophorone diisocyanate, but are not exclusive of other types of polyisocyanates, alternative polyisocyanates being:
the polyisocyanate and/or polyisocyanate component includes one or more polyisocyanates. In some embodiments, the polyisocyanate component includes one or more diisocyanates.
In some embodiments, the polyisocyanate and/or polyisocyanate component comprises an α, ω -alkylene diisocyanate having from 5 to 20 carbon atoms.
Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component includes one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is substantially free or even completely free of aliphatic diisocyanates. In other embodiments, the polyisocyanate component includes one or more aliphatic diisocyanates. In some embodiments, the polyisocyanate component is substantially free, or even completely free, of aromatic diisocyanates.
Examples of useful polyisocyanates include aromatic diisocyanates such as 4,4' -methylenebis (phenyl isocyanate) (MDI), m-Xylene Diisocyanate (XDI), phenylene-1, 4-diisocyanate, naphthalene-1, 5-diisocyanate, and Toluene Diisocyanate (TDI); and isophorone diisocyanate (IPDI), 1, 4-cyclohexyl diisocyanate (CHDI), decane-1, 10-diisocyanate, lysine Diisocyanate (LDI), 1, 4-Butane Diisocyanate (BDI), hexane-1, 6-diisocyanate (HDI), 3' -dimethyl-4, 4' -biphenylene diisocyanate (TODI), 1, 5-Naphthalene Diisocyanate (NDI), dicyclohexylmethane-4, 4' -diisocyanate (H12 MDI), and the like. Mixtures of two or more polyisocyanates may be used. In some embodiments, the polyisocyanate is MDI and/or H12MDI. In some embodiments, the polyisocyanate comprises MDI. In some embodiments, the polyisocyanate comprises H12MDI.
In the polymer, the molar ratio of the polylactic acid dihydric alcohol, the polycaprolactone dihydric alcohol and the 2, 2-dihydroxymethyl butyric acid in the soft segment unit is as follows: 0 to 10:0 to 10:10 to 30 percent.
More preferably, the molar ratio of polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid is as follows: 2 to 8:2 to 8: 12-20;
more preferably, the molar ratio of polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid is as follows: 4 to 6:4 to 6: 12-16;
in the polymer, the weight ratio of the biological polyurethane which is not crosslinked to the carboxymethyl chitosan is 1-2: 2 to 6;
more preferably, the weight ratio of the biological polyurethane which is not crosslinked to the carboxymethyl chitosan is 1.2-1.8: 2 to 4;
more preferably, the weight ratio of the biological polyurethane which is not crosslinked to the carboxymethyl chitosan is 1.4 to 1.6:2.5 to 3.5;
the weight ratio of the biological polyurethane which is subjected to carboxymethyl chitosan crosslinking treatment and is not subjected to carbomer crosslinking treatment to carbomer is 1-4: 0.5 to 1.
In the present invention, any type of carboxymethyl chitosan in the art is optional, and in the examples and comparative examples of the present invention, the carboxymethyl chitosan selected is a model C832672 product offered by Shanghai Milin.
Carbomers in the present invention may be carbomer 340, carbomer 940, carbomer 970, etc., and in the examples and comparative examples of the present invention, carbomer 970 is selected;
meanwhile, the invention also provides a double-network intelligent hydrogel, wherein the active ingredient in the hydrogel is the polymer as described in any one of the above.
In the dual-network intelligent hydrogel, the content of the polymer in the hydrogel is 5-30wt%.
More preferably, the polymer is present in the hydrogel in an amount of 8 to 20wt%;
more preferably, the polymer is present in the hydrogel in an amount of 8 to 12wt%.
Meanwhile, the invention also provides a preparation method of the double-network intelligent hydrogel, which comprises the following steps:
step 1: synthesizing biological polyurethane.
Step 2: under the stirring condition, the biological polyurethane and the sodium chloride aqueous solution of carboxymethyl chitosan are mixed to obtain the first crosslinked network hydrogel.
Step 3: uniformly mixing the carbomer aqueous solution and the first crosslinked network hydrogel, reacting for 3-6 hours at 40-60 ℃, and then soaking in the calcium chloride aqueous solution for 24-48 hours to obtain the double-network intelligent hydrogel.
In practical application, the calcium chloride aqueous solution can be replaced by other ionic compound aqueous solutions, such as ferric trichloride solution and the like;
in the preparation method of the dual-network intelligent hydrogel, the step 1 is as follows: uniformly mixing the soft segment unit and the hard segment unit, and reacting for 2-5 h under the condition of a catalyst at 70-90 ℃; after the reaction is finished, cooling to room temperature, and then dropwise adding triethylamine to obtain biological polyurethane;
the soft segment unit is one or more of polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid; the hard segment unit is isophorone diisocyanate; the mole ratio of the soft segment raw material to the hard segment raw material is 1:1 to 3.
In the preparation method of the dual-network intelligent hydrogel, the molar ratio of the polylactic acid dihydric alcohol, the polycaprolactone dihydric alcohol and the 2, 2-dihydroxymethyl butyric acid in the soft segment unit is as follows: 0 to 10:0 to 10:10 to 30 percent;
the weight ratio of the biological polyurethane to the carboxymethyl chitosan obtained in the step 1 is 1-2: 2 to 6;
the weight ratio of the biological polyurethane to the carbomer obtained by the treatment in the step 2 is 1-4: 0.5 to 1.
More preferably, the preparation method comprises the following steps: (1) Uniformly mixing soft segment units (polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid) and hard segment units (isophorone diisocyanate), and reacting for 2-5 h at 70-90 ℃ under the condition of a catalyst. And after the reaction is finished, cooling to room temperature, and then dropwise adding triethylamine to obtain the biological polyurethane.
(2) Under the condition of intense stirring, the biological polyurethane and the sodium chloride aqueous solution of carboxymethyl chitosan are mixed to obtain the first crosslinked network hydrogel.
(3) And uniformly mixing the carbomer aqueous solution with the first crosslinked network hydrogel, and reacting for 3-6 hours at 40-60 ℃ to obtain the intelligent hydrogel printing ink.
(4) Printing the intelligent hydrogel ink into a precise bionic model by an ink direct-writing printer, and then soaking the model in a calcium chloride aqueous solution for 24-48 hours to obtain the final high bionic intelligent hydrogel model.
The printing parameters are preferably: the diameter of the nozzle of the ink direct-writing printer is 0.2-2.5 mm, the extrusion temperature is 20-40 ℃, the extrusion pressure is 1-20 MPa, and the printing speed is 10-1000 mm/min; the mass concentration of the calcium chloride aqueous solution is 0.5-3 g/100mL of water; the temperature of the model soaked calcium chloride aqueous solution is 20-40 ℃.
Meanwhile, the invention also discloses application of the double-network intelligent hydrogel as printing ink required by the bionic shape model preparation.
One of the above technical solutions of the present invention has at least one of the following advantages or beneficial effects:
compared with the common hydrogel material, the double-network intelligent hydrogel prepared by the method has mechanical properties which are highly similar to those of human skin, and meanwhile, the double-network intelligent hydrogel is highly water-retaining in natural environment so as to keep stable performance and can be degraded.
Compared with the traditional electronic sensing of sensing hydrogel, the intelligent hydrogel prepared by the invention has ion sensing capability and is closer to the sensing mechanism of a human body. The additional thermal actuation capability makes the intelligent hydrogel more biomimetic.
The dual-network intelligent hydrogel prepared by the method can be formed by direct-writing printing of simple, efficient and low-cost ink, and the prepared intelligent hydrogel model has high printing precision and good bionic effect.
The high bionic hand intelligent hydrogel model prepared by the invention can sense external touch sharply and complete the grasping action autonomously, and has the advantages of high reaction speed and good circularity.
Drawings
FIG. 1 is a schematic diagram of the preparation of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model according to examples 1 to 8 of the present invention;
FIG. 2 is a graph showing the mechanical properties of the dual-network smart hydrogel of example 1 of the present invention;
FIG. 3 is a graph showing the water retention performance of the dual-network intelligent hydrogel of example 1 of the present invention at 30 ℃;
FIG. 4 is a graph showing the degradation performance under the condition of the dual-network intelligent hydrogel soil landfill in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the high bionic intelligent hydrogel model in example 1 of the present invention;
FIG. 6 is a schematic diagram of the bionic process of the high bionic intelligent hydrogel model in examples 1 to 8 of the present invention;
FIG. 7 is a scanning electron microscope image of the biopolyurethane/chitosan/carbomer hydrogel model of comparative example 1;
FIG. 8 is a scanning electron micrograph of the biopolyurethane/carbomer hydrogel of comparative example 2;
FIG. 9 is a scanning electron micrograph of a bio-polyurethane/carbomer/carboxymethyl chitosan hydrogel of comparative example 3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to fig. 1, a method for preparing a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 30.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Fig. 2 shows the results of mechanical property test of the smart hydrogel in this example, and the tensile stress strain of the hydrogel is highly similar to that of human skin.
FIG. 3 shows the results of the water retention test of the intelligent hydrogel at 30deg.C, which shows that the high water retention rate of 85.87% can be maintained after 48 hours.
FIG. 4 shows the results of the degradation test of the intelligent hydrogel in this example under the condition of soil landfill, and the hydrogel was basically degraded after 12 months of landfill.
Fig. 5 is a scanning electron microscope image of the high bionic intelligent hydrogel model in this embodiment, and a continuous hole structure in the hydrogel model is obviously observed, so that a channel is provided for ion movement.
Example 2
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) 10.0g of polycaprolactone dihydric alcohol and 0.4g of 2, 2-dimethylolbutyric acid are weighed into a four-necked flask, heated to 50 ℃ and stirred for 30min until the mixture is uniform, 2.8g of isophorone diisocyanate is weighed and added into the four-necked flask, the mixture is uniform, and the reaction is carried out for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=6 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 30.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Example 3
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) 10.0g of polylactic acid dihydric alcohol and 2.2g of 2, 2-dihydroxymethyl butyric acid are weighed into a four-necked flask, heated to 50 ℃ and stirred for 30min until the mixture is uniform, 5g of isophorone diisocyanate is weighed and added into the four-necked flask, the mixture is uniform, and the reaction is carried out for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=8 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 30.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Example 4
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 15.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 3.75g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 1g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Example 5
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 1.5g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 60.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 3g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Example 6
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly 9.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain sodium chloride aqueous solution, and then 15.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 30.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Example 7
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 30.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with a nozzle diameter of 2mm, an extrusion temperature of 50 ℃, an extrusion pressure of 20MPa and a printing speed of 1000mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with a mass concentration of 3g/100ml for 48 hours to obtain the final high-bionic intelligent hydrogel model.
Example 8
A preparation method of a dual-network intelligent hydrogel and a high-bionic intelligent hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 30.0g of carboxymethyl chitosan is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping sodium chloride aqueous solution of carboxymethyl chitosan into a four-neck flask filled with biological polyurethane under a vigorous stirring condition, and obtaining the first crosslinked network hydrogel after vigorously stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the first crosslinked network hydrogel are uniformly mixed, and the mixture is reacted for 6 hours at 50 ℃ to obtain the intelligent hydrogel printing ink.
(4) And printing the intelligent hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 1.52mm, the extrusion temperature of 20 ℃, the extrusion pressure of 1MPa and the printing speed of 10mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 1g/100ml for 12 hours to obtain the final high-bionic intelligent hydrogel model.
Comparative example 1
The preparation method of the biological polyurethane/chitosan/carbomer hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 3.0g of sodium chloride is weighed and dissolved in 300ml of deionized water to obtain a sodium chloride aqueous solution, and then 30.0g of low molecular chitosan (Shanghai microphone, molecular weight 2000) is weighed and dissolved in the sodium chloride aqueous solution. Slowly dripping the sodium chloride aqueous solution of the low molecular chitosan into a four-neck flask filled with biological polyurethane under the condition of intense stirring, and obtaining the biological polyurethane/chitosan hydrogel after intense stirring for 1 h.
(3) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution and the biological polyurethane/chitosan hydrogel are uniformly mixed and reacted for 6 hours at 50 ℃ to obtain the biological polyurethane/chitosan/carbomer hydrogel printing ink.
(4) And printing the biological polyurethane/chitosan/carbomer hydrogel ink into a hand-shaped model by using an ink direct-writing printer with the nozzle diameter of 0.21mm, the extrusion temperature of 30 ℃, the extrusion pressure of 5MPa and the printing speed of 100mm/min, and then soaking the hand-shaped model in a calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the final biological polyurethane/chitosan/carbomer hydrogel model.
Fig. 7 is a scanning electron microscope image of a biological polyurethane/chitosan/carbomer hydrogel model in this comparative example, and it is obvious that the components in the hydrogel model are unevenly distributed, and a continuous pore structure is not formed, so that a channel cannot be provided for ion movement in the sensing process.
Comparative example 2
A method for preparing a hydrogel comprising the steps of:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution is slowly dripped into a four-mouth flask filled with biological polyurethane under the condition of intense stirring, the carbomer aqueous solution is uniformly mixed and then reacts for 6 hours at 50 ℃, and then the carbomer aqueous solution is soaked in calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the biological polyurethane/carbomer hydrogel.
The biological polyurethane/carbomer hydrogel has weak mechanical strength, is easy to break, and cannot be manufactured into a bionic model through ink direct writing printing. Meanwhile, the bio-polyurethane/carbomer hydrogel does not have a thermal actuation capability.
FIG. 8 is a scanning electron microscope image of the biopolyurethane/carbomer hydrogel of the present comparative example, in which it was clearly observed that the hydrogel and the void structure formed therein did not form, and the channel was not provided for ion movement.
Comparative example 3
The preparation method of the biological polyurethane/carbomer/carboxymethyl chitosan hydrogel model comprises the following steps:
(1) Weighing 5.0g of polylactic acid dihydric alcohol, 5.0g of polycaprolactone dihydric alcohol and 1.0g of 2, 2-dihydroxymethyl butyric acid in a four-necked flask, heating to 50 ℃, stirring for 30min until the mixture is uniform, weighing 4g of isophorone diisocyanate, dripping the mixture into the four-necked flask, uniformly mixing, and reacting for 3h under the condition of a catalyst at 80 ℃. After the reaction, cooling to room temperature, and dropwise adding triethylamine until the pH value is=7 to obtain the biological polyurethane.
(2) Firstly, 15.0g of carbomer is weighed and dissolved in 300ml of deionized water to obtain carbomer aqueous solution, the carbomer aqueous solution is slowly dripped into a four-mouth flask filled with biological polyurethane under the condition of intense stirring, the mixture is uniformly mixed and then reacted for 6 hours at 50 ℃, and then the mixture is soaked in calcium chloride aqueous solution with the mass concentration of 2g/100ml for 48 hours to obtain the biological polyurethane/carbomer crosslinked network.
(3) 3.0g of sodium chloride was weighed and dissolved in 300ml of deionized water to obtain an aqueous sodium chloride solution, and then 30.0g of carboxymethyl chitosan was weighed and dissolved in the aqueous sodium chloride solution. And uniformly mixing the sodium chloride aqueous solution of carboxymethyl chitosan with the biological polyurethane/carbomer cross-linked network to obtain the biological polyurethane/carbomer/carboxymethyl chitosan hydrogel.
The biological polyurethane/carbomer/carboxymethyl chitosan hydrogel has weak mechanical strength, is easy to break, and cannot be manufactured into a bionic model through ink direct writing printing. Meanwhile, the bio-polyurethane/carbomer/carboxymethyl chitosan hydrogel does not have a thermal actuation capability. FIG. 9 is a scanning electron microscope image of a biological polyurethane/carbomer/carboxymethyl chitosan hydrogel of this comparative example, where it is evident that the hydrogel has no pore structure formed therein and is unable to provide a channel for ion movement.
Performance testing
1. Stress test hydrogel bars (50 mm. Times.10 mm. Times.0.5 mm) were tensile tested at 25℃using a INSPECT TABLE BLUE KN universal tester at a tensile speed of 10mm/min, and each sample was averaged three times.
2. Moisture retention test records the initial mass W of hydrogel 0 The hydrogel was exposed to a natural environment with 30% humidity and 30 ℃ temperature, and the mass W of the hydrogel was recorded over 48 hours. The formula is used: water retention% 0 The moisture retention of the hydrogels was calculated by x 100%, and each sample was measured three times to average.
3. Residual mass ratio the dried hydrogel was buried in soil, and the initial mass W of the hydrogel was recorded 0 The soil environment humidity is kept at 50% and the temperature is kept at 30 ℃. Hydrogel mass W was recorded over 12 months. The formula is used: residual mass ratio% = W/W 0 The residual mass ratio after hydrogel degradation was calculated by x 100%, and each sample was tested three times for averaging.
4. Conductivity test at room temperatureThe over electrochemical workstation AMETEK 1470E is at 10 6 The hydrogels were tested for ionic conductivity over a frequency range of 1Hz and at a voltage of 10mV, and each sample was averaged three times.
5. The thermal actuation capability test heats the hydrogel to 50 ℃ and observes whether the hydrogel can undergo shape changes autonomously.
The test results can be referred to Table 1
Table 1 test results
| stress/MPa | Moisture retention/% | Residual mass ratio/% | conductivity/S.m -1 | Thermal actuation capability | |
| Example 1 | 1.06 | 85.37 | 4.62 | 8.59 | √ |
| Example 2 | 0.95 | 84.28 | 5.37 | 7.92 | √ |
| Example 3 | 1.37 | 85.12 | 6.86 | 8.01 | √ |
| Example 4 | 1.53 | 86.94 | 5.39 | 6.38 | √ |
| Example 5 | 0.94 | 80.56 | 4.67 | 7.57 | √ |
| Example 6 | 0.88 | 78.39 | 4.75 | 7.92 | √ |
| Example 7 | 1.02 | 85.72 | 4.89 | 8.42 | √ |
| Example 8 | 1.10 | 85.25 | 4.63 | 8.35 | √ |
| Comparative example 1 | 0.83 | 64.36 | 5.96 | 0.84 | √ |
| Comparative example 2 | 0.02 | 26.84 | 3.85 | 0.19 | × |
| Comparative example 3 | 0.07 | 42.56 | 6.94 | 0.37 | × |
Analysis of results
1. By comparing example 1 with comparative example 1, it can be seen that: in comparative example 1, after carboxymethyl chitosan is replaced by low molecular chitosan, the ionic conductivity of the prepared biological polyurethane/chitosan/carbomer hydrogel model is greatly reduced, and the final hydrogel model cannot form a continuous pore structure due to poor compatibility of a low molecular chitosan aqueous solution and neutral biological polyurethane and limited chemical crosslinking degree.
2. By comparing example 1 with comparative example 2, it can be seen that: in comparative example 2, the conductivity of the bio-polyurethane/carbomer single network hydrogel crosslinked only by hydrogen bond and ionic bond is greatly reduced, the thermal actuation capability is not provided, the mechanical property and the water retention performance are greatly reduced, and the bio-polyurethane/carbomer single network hydrogel cannot be prepared into a bionic hydrogel model by an ink direct writing printer. This is all because the lack of chemical cross-linking of carboxymethyl chitosan to bio-polyurethane results in no thermal stimulus response structure formed in the hydrogel, and a single bio-polyurethane/carbomer hydrogel network structure does not provide high mechanical, water retention and ionic conductivity properties to the hydrogel.
3. By comparing example 1 with comparative example 3, it can be seen that: in comparative example 3, the conductive capacity of the bio-polyurethane/carbomer/carboxymethyl chitosan hydrogel after the cross-linking sequence is changed is greatly reduced, the thermal actuation capacity is not provided, the mechanical property is greatly reduced, and the bio-polyurethane/carbomer/carboxymethyl chitosan hydrogel cannot be prepared into a bionic hydrogel model through an ink direct-writing printer. This is because carbomer occupies the active site of the bio-polyurethane after forming a crosslinked network with the bio-polyurethane, making it difficult for carboxymethyl chitosan to further react chemically with the bio-polyurethane to form a second crosslinked network. Therefore, the thermal stimulus response internal stress in the hydrogel is limited, and the mechanical properties, the water retention property and the ion conductivity are not as good as those of example 1.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (7)
1. The polymer capable of generating the high bionic intelligent hydrogel is characterized by comprising biological polyurethane, wherein the biological polyurethane is subjected to crosslinking treatment by carboxymethyl chitosan and carbomer; wherein the biological polyurethane and carboxymethyl chitosan are chemically crosslinked, and the biological polyurethane and carbomer realize surface crosslinking through hydrogen bond and ionic bond;
the weight ratio of the biological polyurethane which is not subjected to crosslinking treatment to the carboxymethyl chitosan is 1-2: 2-6;
the weight ratio of the biological polyurethane which is subjected to carboxymethyl chitosan crosslinking treatment and is not subjected to carbomer crosslinking treatment to carbomer is 1-4: 0.5-1;
the biological polyurethane consists of a soft segment unit and a hard segment unit; the soft segment unit is polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid; the hard segment unit is isophorone diisocyanate; the mole ratio of the soft segment raw material to the hard segment raw material is 1: 1-3, wherein the mole ratio of polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid in the soft segment unit is as follows: 2-8: 2-8: 12-20.
2. The polymer according to claim 1, wherein the weight ratio of the non-crosslinked bio-polyurethane to the carboxymethyl chitosan is 1.2-1.8: 2-4.
3. A dual-network intelligent hydrogel, characterized in that the active ingredient in the hydrogel is the polymer as claimed in claim 1 or 2.
4. The dual-network intelligent hydrogel according to claim 3, wherein the content of the polymer in the hydrogel is 5-30wt%.
5. A method for preparing the dual-network intelligent hydrogel according to claim 3 or 4, comprising the following steps:
step 1: synthesizing biological polyurethane;
step 2: under the stirring condition, mixing biological polyurethane with sodium chloride aqueous solution of carboxymethyl chitosan to obtain first crosslinked network hydrogel;
step 3: uniformly mixing a carbomer aqueous solution and a first crosslinked network hydrogel, reacting for 3-6 hours at 40-60 ℃, and then soaking in a calcium chloride aqueous solution for 24-48 hours to obtain a double-network intelligent hydrogel;
the weight ratio of the biological polyurethane to the carboxymethyl chitosan obtained in the step 1 is 1-2: 2-6;
the weight ratio of the biological polyurethane to the carbomer obtained by the treatment in the step 2 is 1-4: 0.5 to 1.
6. The method for preparing a dual-network intelligent hydrogel according to claim 5, wherein the step 1 is: uniformly mixing the soft segment unit and the hard segment unit, and reacting for 2-5 hours at the temperature of 70-90 ℃ under the condition of a catalyst; after the reaction is finished, cooling to room temperature, and then dropwise adding triethylamine to obtain biological polyurethane;
the soft segment unit is polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid; the hard segment unit is isophorone diisocyanate; the molar ratio of soft segment units to hard segment units is 1: 1-3, wherein the mole ratio of polylactic acid dihydric alcohol, polycaprolactone dihydric alcohol and 2, 2-dihydroxymethyl butyric acid in the soft segment unit is as follows: 2-8: 2-8: 12-20.
7. Use of the dual network intelligent hydrogel of claim 3 or 4 as a biomimetic model to prepare a desired 3D/4D printing ink.
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