CN113480745B - Super-stretching magnetic response self-repairing hydrogel and preparation method and application thereof - Google Patents

Super-stretching magnetic response self-repairing hydrogel and preparation method and application thereof Download PDF

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CN113480745B
CN113480745B CN202110411457.1A CN202110411457A CN113480745B CN 113480745 B CN113480745 B CN 113480745B CN 202110411457 A CN202110411457 A CN 202110411457A CN 113480745 B CN113480745 B CN 113480745B
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侯昭升
滕金伟
刘常琳
徐钧
毕晶晶
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Wuxi Xiangyuan Information Technology Co ltd
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Abstract

The invention belongs to the field of high polymer materials, and discloses a hyper-tensile magnetic response self-repairing hydrogel as well as a preparation method and application thereof. The hydrogel internally contains a double-crosslinked network structure, and due to the existence of metal coordination bonds, the energy of a polymer can be effectively dispersed when the hydrogel is stressed, so that the covalent crosslinked network is prevented from being damaged, and meanwhile, the second network with higher toughness can ensure the integrity of the hydrogel when the second network deforms. In addition, the magnetic nanoparticles form a gel network through imine bonds, the composite structure is stable, the problem that the magnetic nanoparticles are easy to fall off in common physical blending is solved, and the imine bonds endow the material with self-repairing performance.

Description

Super-stretching magnetic response self-repairing hydrogel and preparation method and application thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a hyper-tensile and magnetic response self-repairing polyurethane hydrogel and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Rigid robots have been widely used in the fields of industry, medical treatment, military and the like, but due to their fixed structure, they cannot be precisely controlled in a special environment to achieve expected work, and therefore, they have poor environmental adaptability, while soft robots are gradually becoming the dominant force for robot development as a new generation of robots, and their use and status are gradually replacing traditional rigid robots. Compared with the prior art, the soft robot has more driving mode types and degrees of freedom in operation, more flexible movement and better environmental adaptability and safety.
The hydrogel is a functional polymer material which has a three-dimensional network structure, retains a large amount of water while maintaining the structure of the hydrogel, and can be dehydrated and deswelled under certain conditions, wherein the hydrogel which can respond to external environmental stimuli is also called intelligent hydrogel. As a candidate material for making a software robot in a new era, the intelligent hydrogel has inherent advantages due to high water content, flexibility, responsiveness and the like. Magnetic hydrogel as an intelligent hydrogel can be deformed under the induction of the change of an external magnetic field, when the hydrogel is placed in the magnetic field, magnetic particles are gathered due to mutual attraction, the aperture of the hydrogel is reduced, and the volume of the hydrogel is changed, otherwise, when the magnetic field is closed, the hydrogel is restored to the original state. The magnetic hydrogel can be stretched, contracted and curled under the magnetic field, and magnetic drive is favored by the drive control of intelligent flexible materials by utilizing the characteristics of various deformation modes and the harmlessness of the magnetic field and the remote control, such as Ramanujan and the like which utilize different Fe3O4The composite gel with different contents has the characteristics of different magnetic field thresholds, and the PVA/Fe capable of simulating the bending of human fingers is prepared3O4Magnetic propertyA hydrogel.
The preparation of magnetic hydrogels focuses mainly on the following strategies: firstly, magnetic particles are generated in situ in a gel network, and the method for preparing the magnetic hydrogel can ensure that a large amount of magnetic components are introduced and are uniformly dispersed in the gel network, which is the advantage of the method; the disadvantages are that the process is slightly complicated, the period is long, the production efficiency is low, and the polymer network structure is often damaged to a certain extent to cause poor mechanical property; secondly, the ready-made magnetic particles are introduced into the gel network, and the process is simple, easy to operate and high in preparation speed. But the magnetic nano particles can not be ensured not to be agglomerated and uniformly dispersed in the system; thirdly, the magnetic particles directly participate in the gel forming process, and by adopting the technology, the magnetic particles directly participate in the hydrogel forming process, and the structural components of the traditional chemical cross-linking agent are not complex. Furthermore, there is a chemical bond between the magnetic particles and the gel network, the magnetic particles have definite positioning in the network, and the composite structure should be very stable.
The inventor finds that most of the previous magnetic hydrogels have extremely poor mechanical properties, are easy to break and fracture when stressed, cannot return to the original shape, and limit the practical application of the magnetic hydrogels in soft materials. In addition, the gel material generates small cracks and gaps which are difficult to detect when being damaged, if the gel material cannot be repaired in time, the service life of the material is seriously shortened, and the maintenance cost of the soft robot is increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a hyper-tensile magnetic-response hydrogel capable of self-repairing and a preparation method thereof. Polyurethane as a hydrogel matrix can provide good toughness and tear resistance. Firstly, aldehyde-terminated polyurethane with a side chain containing pyridyl is synthesized, amino modified magnetic nano particles are crosslinked in the presence of iron ions, and the hyperextension magnetic response self-repairing hydrogel is obtained after treatment. The hydrogel internally contains a double-crosslinked network structure, and due to the existence of metal coordination bonds, the energy of a polymer can be effectively dispersed when the hydrogel is stressed, so that the covalent crosslinked network is prevented from being damaged, and meanwhile, the second network with higher toughness can ensure the integrity of the hydrogel when the second network deforms. In addition, the magnetic nanoparticles form a gel network through imine bonds, the composite structure is stable, the problem that the magnetic nanoparticles are easy to fall off in common physical blending is solved, and the imine bonds endow the material with self-repairing performance.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a hyperextension magnetic response self-repairing hydrogel, which comprises the following steps:
the aldehyde-terminated polyurethane with the side chain containing pyridyl is crosslinked with the amino-modified magnetic nanoparticles in the presence of iron ions to obtain polyurethane gel;
and (3) replacing the polyurethane gel in a solvent of ferric salt to obtain the hyperextension self-repairing magnetic polyurethane hydrogel.
The invention combines the toughening method of the hydrogel with the preparation method of the magnetic hydrogel to prepare the magnetic hydrogel with high toughness and self-repairing capability.
In a second aspect of the present invention, there is provided a hyper-stretched magnetically responsive self-repairing hydrogel prepared by any of the above methods.
In a third aspect of the invention, the application of the hyperextension magnetic response self-repairing hydrogel in the fields of soft robots, bionics, industry, medical treatment and military affairs is provided.
The fourth invention of the invention provides aldehyde-terminated polyurethane with a side chain containing pyridyl, and the structural formula is as follows:
Figure GDA0003173060940000041
wherein R is1Linear or branched alkyl selected from C1-C6, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted methylcyclopentyl, substituted or unsubstituted ethylcyclopentyl, substituted or unsubstituted methylcyclohexyl, substituted or unsubstituted ethylcyclohexyl, di-p-tolylmethyl, di-p-tolylethyl;
the substitution is selected from C1-C6 straight chain or branched chain alkyl, alkoxy, single substitution or multiple substitution;
n＝20-90，m＝1-5，p＝2-8。
in a fifth aspect of the present invention, there is provided a method for preparing an aldehyde-terminated side-chain pyridine-group-containing polyurethane, comprising: and (2) reacting the isocyanate-terminated polyurethane prepolymer with ethylenediamine, and adding a glyoxal compound to react to obtain aldehyde-terminated pyridine-based polyurethane APy-PU after the reaction is finished.
The invention has the beneficial effects that:
(1) the hydrogel provided by the invention has higher tensile length, and the highest elongation can reach 1600%.
(2) The hydrogel provided by the invention has superparamagnetism, and the change of the magnetic force can be obviously caused by the tiny change of the external magnetic field.
(3) The hydrogel provided by the invention adopts a double-crosslinked network structure, contains reversible metal coordination bonds, and has good stretching resilience.
(4) The hydrogel provided by the invention has good self-healing performance, the healing efficiency is close to 100% within 30 minutes at the fastest speed, the service life of the material is greatly prolonged, and the burden of frequently replacing the material is solved.
(5) The hydrogel provided by the invention can be used as a soft material to realize magnetic driving of an intelligent robot or a magnetic medical catheter.
(6) The operation method is simple, low in cost, universal and easy for large-scale production.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is a graph of uniaxial extension-relaxation cycles of hydrogels of different pyridyl content prepared in examples 1,2, and 3 of the present invention.
FIG. 2 shows different Fe contents prepared in examples 1,5 and 6 of the present invention3O4Hydrogel hysteresis curve of nanoparticles.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect of the present invention, there is provided an aldehyde-terminated polyurethane having a side chain containing pyridyl groups, the structural formula of which is as follows:
Figure GDA0003173060940000061
wherein R is1Linear or branched alkyl selected from C1-C6, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted methylcyclopentyl, substituted or unsubstituted ethylcyclopentyl, substituted or unsubstituted methylcyclohexyl, substituted or unsubstituted ethylcyclohexyl, di-p-tolylmethyl, di-p-tolylethyl;
the substitution is selected from C1-C6 straight chain or branched chain alkyl, alkoxy, single substitution or multiple substitution;
n＝20-90，m＝1-5，p＝2-8。
in one or more embodiments of the invention, R is1The substituent is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, 1,2 phenyl, 1,3 phenyl, 1,4 phenyl and 1,3 substituted phenyl, the substitution is selected from C1-C6 straight chain or branched chain alkyl and alkoxy, and is mono-substituted or multi-substituted, the substitution site is 4, 5 and 6, preferably 4;
the substitution is more preferably 4-methyl, 4-ethyl, 4-propyl, 4-isopropyl;
in some embodiments, R1Selected from substituted or unsubstituted 1-methyl-3-cyclopentyl alkyl, substituted or unsubstituted 1-ethyl-3-cyclopentyl alkyl, substituted or unsubstituted 1-methyl-3-cyclohexyl alkyl, and substituted or unsubstituted 1-ethyl-3-cyclohexyl alkyl, wherein the substitution is preferably 1,5, 5-trimethyl substitution;
in some embodiments of the present invention, the,
R1is selected from
Figure GDA0003173060940000071
In a second aspect of the present invention, there is provided a method for preparing an aldehyde-terminated side-chain pyridine-group-containing polyurethane, the method comprising:
(1) dissolving a certain amount of diisocyanate, polyethylene glycol, a dihydroxypyridine compound (PyDH) and a catalyst in an organic solvent, stirring, and reacting at constant temperature to obtain an isocyanate end-capped polyurethane prepolymer solution.
(2) And (2) adding ethylenediamine into the reaction solution obtained in the step (1) under vigorous stirring, continuously stirring until the reaction is finished, finally adding glyoxal compound for reaction to obtain aldehyde-terminated pyridyl polyurethane (APy-PU), and purifying.
In some embodiments, the diisocyanate in the step (1) is aliphatic diisocyanate and aromatic diisocyanate, and is further preferably aliphatic diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate;
in some embodiments, the molecular weight of the polyethylene glycol in step (1) is 4000-;
in some embodiments, the dihydroxypyridine compound (PyDH) used in step (1) above is prepared according to the method disclosed in patent CN 110483740A. The structural formula of the dihydroxypyridine compound is as follows:
Figure GDA0003173060940000072
in some embodiments, the catalyst described in the above step (1) is a tin-based catalyst, further preferably diisobutyltin dilaurate or stannous octoate;
in some embodiments, the solvent described in step (1) above is N, N-Dimethylformamide (DMF);
in some embodiments, the molar ratio of polyethylene glycol to PyDH described in step (1) above is 1:0.5 to 1: 1;
in some embodiments, the diisocyanate added in step (1) above has a molar ratio of-NCO to-OH of 1:0.7 to 1: 0.9;
in some embodiments, the amount of the catalyst added in the step (1) is 0.3-1% of the total mass of the feed;
in some embodiments, the amount of solvent used in step (1) above is such that 0.5 to 1g of total reactants are dissolved per 1mL of solvent;
in some embodiments, the reaction temperature in step (1) is 60-80 deg.C, more preferably 65-70 deg.C, the reaction end point is determined by di-n-butylamine titration to reach the theoretical-NCO content, the reaction time is about 2-4h,
in some embodiments, the molar amount of ethylenediamine and glyoxal in step (2) above is calculated as follows:
namines as pesticides＝nAldehydes＝2×(nDiisocyanate-nPolyethylene glycol-nDihydroxypyridines)。
In some embodiments, the reaction temperature is controlled to 10-30 ℃ after the diamino compound is added in step (2), and the reaction time is 3-4 hours.
In some embodiments, the reaction temperature is controlled to 15 to 35 ℃ after the dialdehyde compound is added in step (2), and the reaction time is 3 to 4 hours.
In some embodiments, the purification method of APy-PU in step (2) is: APy-PU is diluted to 0.05g/mL by DMF, then is settled by octoploid glacial ethyl ether (-5-0 ℃) and is dried in vacuum at normal temperature to constant weight after suction filtration.
In a third aspect of the present invention, a hyperextension responsive self-healing hydrogel is provided.
In a fourth aspect of the present invention, there is provided a method for preparing a hyper-stretch responsive self-healing hydrogel, the method comprising:
modifying amino group with Fe3O4And (3) ultrasonically dispersing the nano particles in a DMF solution, adding the DMF solution of APy-PU, uniformly stirring, and standing to obtain the polyurethane gel. The prepared polyurethane gel is placed in FeSO4Soaking in water solution, and periodically replacing deionized water to obtain the hyperextension self-repairing magnetic polyurethane hydrogel.
In some embodiments, the amino-modified Fe described above3O4The particle diameter of the nano-particles is about 25-80 nm, and the content of surface amino groups is about 3000 +/-300 mu mol g-1；
In some embodiments, the concentration of the DMF solution is 0.3-0.5 g/ml APy-PU;
in some embodiments, the above-described FeSO4The concentration of the aqueous solution is 0.0002-0.001mol/L, and the volume is 500-1000 mL.
In some embodiments, the amino-modified Fe described above3O4The molar ratio of amino on the surfaces of the nanoparticles to aldehyde groups in the APy-PU is 1: 1;
in some embodiments, the Fe is as described above3O4The mass concentration of the nano particles in the DMF solution is 0.5-2 g/L;
in some embodiments, the standing condition is standing reaction at 30-50 ℃ for 15-20h, and more preferably at 40 ℃ for 18 h;
in some embodiments, the gel is in FeSO4Soaking time in the aqueous solution and deionized water is 10-15 h; the deionized water is replaced 3-5 times.
Preparation of magnetic nanoparticles according to the literature (Lei Yang et al Preparation of novel hydrophilic magnetic Fe)3O4Water borne polyurethane nanocomposites. journal of Applied Polymer Science,2020,137(15):48546) and incorporated herein in its entirety by the following method:
0.54g of ferrous chloride tetrahydrate and 1.42g of ferric chloride hexahydrate as a solid were dissolved in 160mL of deionized water at 80 ℃. Adding 1, 6-hexamethylene diamine into the solution under the action of ultrasonic waves, stirring for 1.5h, and keeping the reaction temperature of the mixture at 80 ℃ for full reaction. After the reaction is finished, separating the amino modified magnetic nanoparticles from the reaction system by using a magnetic separation technology for 6h, washing the amino modified magnetic nanoparticles with deionized water and ethanol for three times, and drying the amino modified magnetic nanoparticles for 12h at 50 ℃ under a vacuum condition.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
In the following examples, amino-modified Fe3O4The preparation method of the nano particles comprises the following steps: 0.54g of ferrous chloride tetrahydrate and 1.42g of ferric chloride hexahydrate as a solid were dissolved in 160mL of deionized water at 80 ℃. Adding 1, 6-hexamethylene diamine into the solution under the action of ultrasonic waves, stirring for 1.5h, and keeping the reaction temperature of the mixture at 80 ℃ for full reaction. After the reaction is finished, separating the amino modified magnetic nanoparticles from the reaction system by using a magnetic separation technology for 6h, washing the amino modified magnetic nanoparticles with deionized water and ethanol for three times, and drying the amino modified magnetic nanoparticles for 12h at 50 ℃ under a vacuum condition.
Example 1
The polyurethane is prepared by dissolving 3.03g of hexamethylene diisocyanate, 80.00g of polyethylene glycol (8000 g/mol of number average molecular weight), 1.07g of dihydroxypyridine (PyDH) and 0.5g of stannous isooctanoate in 100mL of N, N-Dimethylformamide (DMF), adding into a three-neck flask, heating in an oil bath to 70 ℃ for constant temperature reaction until the-NCO content in the system measured by a di-N-butylamine method reaches the theoretical value, and reacting for about 2.5 h. After cooling to room temperature, 0.36g of ethylenediamine was added dropwise with stirring, and the reaction was carried out while maintaining the temperature at 23 ℃ until the absorption peak of-NCO in the FT-IR spectrum disappeared in about 4 hours. Continuously dropwise adding 0.35g of glyoxal into the reaction bottle, heating to 30 ℃, and reacting for 3.5 hours at constant temperature. And after the reaction is finished, cooling to room temperature, adding a certain amount of DMF (dimethyl formamide) to dilute the product to 0.05g/mL, then using eight times of ethyl glacial ether to settle, performing suction filtration, and performing vacuum drying at room temperature to constant weight to obtain the aldehyde-terminated pyridyl polyurethane (APy-PU).
Preparation of hydrogel 0.24g of amino-modified Fe3O4Ultrasonically dispersing nano particles in 200mL of DMF solution, dissolving 10g of APy-PU in 30mL of DMF, uniformly mixing and stirring the two solutions, standing the mixture at 30 ℃ for 20 hours to obtain polyurethane gel, and soaking the polyurethane gel in 500mL of FeSO with the concentration of 0.0003mol/L4And (3) replacing the aqueous solution with the same volume once every 10 hours, and repeating for 3 times to obtain the hyperextension self-repairing magnetic polyurethane hydrogel. Designated hydrogel W1.
Example 2
The polyurethane is prepared by dissolving 3.03g of hexamethylene diisocyanate, 72.00g of polyethylene glycol (8000 g/mol of number average molecular weight), 1.28g of dihydroxypyridine (PyDH) and 0.6g of stannous isooctanoate in 100mL of N, N-Dimethylformamide (DMF), adding into a three-neck flask, heating in an oil bath to 75 ℃ for reaction at a constant temperature until the-NCO content in the system measured by a di-N-butylamine method reaches a theoretical value, and reacting for about 2 hours. After cooling to room temperature, 0.36g of ethylenediamine was added dropwise with stirring, and the reaction was carried out while maintaining the temperature at 20 ℃ until the absorption peak of-NCO in the FT-IR spectrum disappeared in about 3.5 hours. 0.35g of glyoxal is continuously dripped into the reaction bottle, and the temperature is raised to 40 ℃ for constant-temperature reaction for 3.5 h. And after the reaction is finished, cooling to room temperature, adding a certain amount of DMF (dimethyl formamide) to dilute the product to 0.05g/mL, then using eight times of ethyl glacial ether to settle, performing suction filtration, and performing vacuum drying at room temperature to constant weight to obtain the aldehyde-terminated pyridyl polyurethane (APy-PU).
Preparation of hydrogel 0.26g of amino-modified Fe3O4Ultrasonically dispersing nano particles in 200mL of DMF solution, dissolving 10g of APy-PU in 30mL of DMF, uniformly mixing and stirring the two solutions, standing the mixture at 30 ℃ for 15 hours to obtain polyurethane gel, and soaking the polyurethane gel in 500mL of FeSO with the concentration of 0.0004mol/L4And (3) replacing the aqueous solution with the same volume once every 12h, and repeating for 3 times to obtain the hyperextension self-repairing magnetic polyurethane hydrogel. Designated hydrogel W2.
Example 3
The polyurethane is prepared by dissolving 3.03g of hexamethylene diisocyanate, 64.00g of polyethylene glycol (8000 g/mol of number average molecular weight), 1.50g of dihydroxypyridine (PyDH) and 0.6g of stannous isooctanoate in 100mL of N, N-Dimethylformamide (DMF), adding into a three-necked flask, heating in an oil bath to 80 ℃ for constant temperature reaction until the-NCO content in the system measured by a di-N-butylamine method reaches the theoretical value, and reacting for about 1.5 h. After cooling to room temperature, 0.36g of ethylenediamine was added dropwise with stirring, and the reaction was carried out while maintaining the temperature at 30 ℃ until the absorption peak of-NCO in the FT-IR spectrum disappeared in about 3 hours. Continuously dropwise adding 0.35g of glyoxal into the reaction bottle, heating to 35 ℃, and reacting for 3 hours at constant temperature. And after the reaction is finished, cooling to room temperature, adding a certain amount of DMF (dimethyl formamide) to dilute the product to 0.05g/mL, then using eight times of ethyl glacial ether to settle, performing suction filtration, and performing vacuum drying at room temperature to constant weight to obtain the aldehyde-terminated pyridyl polyurethane (APy-PU).
Preparation of hydrogel 0.29g of amino-modified Fe3O4Ultrasonically dispersing the nano particles in 200mL of DMF solution, dissolving 10g of APy-PU in 30mL of DMF, uniformly mixing and stirring the two solutions, standing the mixture at 30 ℃ for 18 hours to obtain polyurethane gel, and soaking the polyurethane gel in 500mL of FeSO with the concentration of 0.0005mol/L4And (3) replacing the aqueous solution with the same volume once every 12 hours, and repeating for 3 times to obtain the hyperextension self-repairing magnetic polyurethane hydrogel. Designated hydrogel W3.
Example 4
6.22g of isophorone diisocyanate, 120.00g of polyethylene glycol (with the number average molecular weight of 12000g/mol), 2.13g of dihydroxypyridine (PyDH) and 1g of stannous isooctanoate are dissolved in 130mL of N, N-Dimethylformamide (DMF), and then the mixture is added into a three-neck flask, heated in an oil bath to 75 ℃ for constant-temperature reaction until the content of-NCO in the system measured by a di-N-butylamine method reaches a theoretical value, and the reaction lasts for about 2 hours. After cooling to room temperature, 0.96g of ethylenediamine was added dropwise with stirring, and the reaction was carried out while maintaining the temperature at 15 ℃ until the absorption peak of-NCO in the FT-IR spectrum disappeared in about 4 hours. And continuously dropwise adding 0.92g of glyoxal into the reaction bottle, heating to 15 ℃, and reacting for 4 hours at constant temperature. And after the reaction is finished, cooling to room temperature, adding a certain amount of DMF (dimethyl formamide) to dilute the product to 0.05g/mL, then using eight times of ethyl glacial ether to settle, performing suction filtration, and performing vacuum drying at room temperature to constant weight to obtain the aldehyde-terminated pyridyl polyurethane (APy-PU).
Preparation of hydrogel 0.42g of amino-modified Fe3O4Ultrasonically dispersing nano particles in 300mL of DMF solution, dissolving 10g of APy-PU in 30mL of DMF, uniformly mixing and stirring the two solutions, standing the mixture at 30 ℃ for 15 hours to obtain polyurethane gel, and soaking the polyurethane gel in 1000mL of FeSO with the concentration of 0.0002mol/L4The water solution is replaced once every 12h by the same volume of water solutionAnd repeating the steps for 3 times to obtain the hyperextension self-repairing magnetic polyurethane hydrogel. Designated hydrogel W4.
Example 5
The polyurethane is prepared by dissolving 3.53g hexamethylene diisocyanate, 80.00g polyethylene glycol (8000 g/mol number average molecular weight), 1.07g dihydroxypyridine (PyDH) and 0.6g stannous isooctanoate in 130mL N, N-dimethyl formamide (DMF), adding into a three-neck flask, heating in oil bath to 75 ℃ for constant temperature reaction until the-NCO content in the system measured by a di-N-butylamine method reaches the theoretical value, and reacting for about 2 h. After cooling to room temperature, 0.72g of ethylenediamine was added dropwise with stirring, and the reaction was carried out while maintaining the temperature at 25 ℃ until the-NCO absorption peak in the FT-IR spectrum disappeared in about 3.5 hours. And continuously dropwise adding 0.70g of glyoxal into the reaction bottle, heating to 35 ℃, and reacting for 3 hours at constant temperature. And after the reaction is finished, cooling to room temperature, adding a certain amount of DMF (dimethyl formamide) to dilute the product to 0.05g/mL, then using eight times of ethyl glacial ether to settle, performing suction filtration, and performing vacuum drying at room temperature to constant weight to obtain the aldehyde-terminated pyridyl polyurethane (APy-PU).
Preparation of hydrogel 0.47g of amino-modified Fe3O4Ultrasonically dispersing nano particles in 300mL of DMF solution, dissolving 10g of APy-PU in 30mL of DMF, uniformly mixing and stirring the two solutions, standing the mixture at 30 ℃ for 14 hours to obtain polyurethane gel, and soaking the polyurethane gel in 500mL of FeSO with the concentration of 0.0003mol/L4And (3) replacing the aqueous solution with the same volume once every 11 hours, and repeating for 3 times to obtain the hyperextension self-repairing magnetic polyurethane hydrogel. Designated hydrogel W5.
Example 6
The polyurethane is prepared by dissolving 4.04g hexamethylene diisocyanate, 80.00g polyethylene glycol (8000 g/mol number average molecular weight), 1.07g dihydroxypyridine (PyDH) and 0.6g stannous isooctanoate in 130mL N, N-dimethyl formamide (DMF), adding into a three-neck flask, heating in an oil bath to 75 ℃ for constant temperature reaction until the-NCO content in the system measured by a di-N-butylamine method reaches the theoretical value, and reacting for about 2 hours. After cooling to room temperature, 1.08g of ethylenediamine was added dropwise with stirring, and the reaction was carried out while maintaining the temperature at 25 ℃ until the-NCO absorption peak in the FT-IR spectrum disappeared in about 3.0 hours. And continuously dropwise adding 1.04g of glyoxal into the reaction bottle, heating to 15 ℃, and reacting for 4 hours at constant temperature. And after the reaction is finished, cooling to room temperature, adding a certain amount of DMF (dimethyl formamide) to dilute the product to 0.05g/mL, then using eight times of ethyl glacial ether to settle, performing suction filtration, and performing vacuum drying at room temperature to constant weight to obtain the aldehyde-terminated pyridyl polyurethane (APy-PU).
Preparation of hydrogel 0.71g of amino-modified Fe3O4Ultrasonically dispersing nano particles in 400mL of DMF solution, dissolving 10g of APy-PU in 30mL of DMF, uniformly mixing and stirring the two solutions, standing the mixture at 30 ℃ for 16 hours to obtain polyurethane gel, and soaking the polyurethane gel in 700mL of FeSO with the concentration of 0.0002mol/L4And (3) replacing the aqueous solution with the same volume once every 12 hours, and repeating for 3 times to obtain the hyperextension self-repairing magnetic polyurethane hydrogel. Designated hydrogel W6.
Analysis and description: the following analytical methods were used for all examples unless otherwise indicated.
And (3) testing tensile property: the hydrogel was cut into standard dumbbells of approximately 1mm thickness and tested for tensile properties by means of a biomechanical tensile machine (Instron-5944) with both tensile and relaxation rates of 5-6 mm/min. In addition, toughness can be characterized by the work produced in the unit volume of the hydrogel by external forces at the time of fracture of the hydrogel, obtained by integration under the stress-strain curve of pulling to elongation to fracture.
Self-healing performance test tensile bars (60X 10X 3mm) of hydrogel W1 were placed on a glass plate, the bars were cut from the middle, the two cut-off hydrogel bars were aligned along the incision to make a tight fit, and then placed at room temperature, followed by tensile testing of the healed bars every 5 minutes, with the experimental results shown in Table 1.
The self-healing efficiency R is represented by the formula: r ═ σ1/σ0Where σ is0、σ1The tensile strengths before and after self-repair are respectively.
Table 1: repair efficiency of hydrogel W1 at various times
Figure GDA0003173060940000141
As can be seen from Table 1, the hydrogel has the fastest self-repairing rate in the first 10 minutes, the repairing efficiency can reach more than 50 percent, which shows that the hydrogel has good self-repairing performance, the repairing efficiency can be as close to 100 percent within 30 minutes as fast as possible,
the tensile properties of the hydrogels W1, W2 and W3 are respectively measured, and the tensile relaxation curves of the hydrogels are shown in fig. 1, so that the elongation of the hydrogels with different pyridyl contents can reach more than 1500%, and the hydrogels have better tensile properties, because the internal structure of the hydrogel is a double-crosslinked network structure and simultaneously contain dynamic reversible covalent bonds and non-covalent bonds. The metal coordination bond as a sacrificial bond can effectively dissipate energy when stressed, thereby preventing the breakage of covalent bonds and maintaining a network structure. In addition, the hydrogel can rapidly recover the original appearance after being stretched and has good resilience, because the metal coordination bonds in the hydrogel are re-complexed after the stress is finished. The higher the content of the pyridyl group, the stronger the toughness, which indicates that the energy dissipation is related to the dissociation-coordination of the complex, so that the toughness of the hydrogel can be controlled by adjusting the content of the pyridyl group to meet specific requirements.
Magnetic response property: the magnetic properties of the hydrogel were analyzed using a vibrating sample magnetometer. The hysteresis curves of different hydrogels are shown in FIG. 2, in which W1, W5, and W6 represent Fe respectively3O4The hydrogel prepared by the nano particle content of 2.4%, 4.7% and 7.1% can be found from figure 2, the hydrogel has a superparamagnetic characteristic, and the saturation magnetization of the hydrogel is along with Fe3O4The content of the nano particles is increased, which shows that the prepared hydrogel has more sensitive magnetic response performance. This is because under the action of the magnetic field, each magnetized particle has the same magnetic induction line direction, and is mutually superposed and transmitted, so that the hydrogel has magnetic permeability. At the same time, Fe3O4The hydrogel with high nano particle content has more magnetized particles, thereby showing higher magnetization intensity, so that the control of Fe can be realized3O4The content of the nano-particles in the hydrogel controls the magnetic properties of the hydrogel.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (12)

1. A preparation method of a hyperextension magnetic response self-repairing hydrogel is characterized by comprising the following steps:
crosslinking aldehyde-terminated polyurethane with a side chain containing pyridyl with amino-modified magnetic nanoparticles to obtain polyurethane gel;
replacing the polyurethane gel in a solvent of ferric salt to obtain the hyperextension self-repairing magnetic polyurethane hydrogel;
the structural formula of the aldehyde-terminated polyurethane with the side chain containing pyridyl is as follows:
Figure FDA0003679191190000011
wherein R is1Linear or branched alkyl selected from C1-C6, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted methylcyclopentyl, substituted or unsubstituted ethylcyclopentyl, substituted or unsubstituted methylcyclohexyl, substituted or unsubstituted ethylcyclohexyl, di-p-tolylmethyl, di-p-tolylethyl;
the substitution is selected from C1-C6 straight chain or branched chain alkyl, alkoxy, single substitution or multiple substitution;
n, m and p are natural numbers larger than zero.
2. The overpull of claim 1The preparation method of the extensional magnetic response self-repairing hydrogel is characterized in that the amino modified magnetic nanoparticles are amino modified Fe3O4Nanoparticles.
3. The method for preparing the hyperextension magnetic response self-repairing hydrogel of claim 2, wherein the amino modified Fe3O4The particle diameter of the nano particles is 25-80 nm, and the content of surface amino groups is 3000 +/-300 mu mol g-1。
4. The method for preparing the hyperextension magnetic response self-repairing hydrogel of claim 1, wherein R is1Is selected from methyl, ethyl, propyl, butyl, amyl, hexyl, 1,2 phenyl, 1,3 phenyl, 1,4 phenyl and 1,3 substituted phenyl, wherein the substitution is selected from C1-C6 straight-chain or branched-chain alkyl and alkoxy, and is single-substituted or multi-substituted, and the substitution site is 4, 5 or 6.
5. The method for preparing the hyperextension magnetic response self-repairing hydrogel as claimed in claim 4, wherein the substitution is 4-methyl, 4-ethyl, 4-propyl or 4-isopropyl.
6. The method for preparing the hyperextension magnetic response self-repairing hydrogel of claim 1, wherein R is R1Selected from the group consisting of substituted or unsubstituted 1-methyl-3-cyclopentyl alkyl, substituted or unsubstituted 1-ethyl-3-cyclopentyl alkyl, substituted or unsubstituted 1-methyl-3-cyclohexyl, and substituted or unsubstituted 1-ethyl-3-cyclohexyl.
7. The method for preparing the hyperextension magnetic response self-repairing hydrogel as claimed in claim 6, wherein the substitution is 1,5, 5-trimethyl substitution.
8. The method for preparing the hyperextension magnetic response self-repairing hydrogel of claim 1, wherein R is R1Is selected from- (CH) — (CH)2)4—、—(CH2)6—、
Figure FDA0003679191190000021
Figure FDA0003679191190000031
9. The method for preparing the hyperextension magnetic response self-repairing hydrogel as claimed in claim 1, wherein n is 20-90, m is 1-5, and p is 2-8.
10. The method for preparing the hyperextension magnetic response self-repairing hydrogel as claimed in claim 1, wherein the preparation method of the aldehyde-terminated polyurethane with the side chain containing pyridyl comprises the steps of reacting isocyanate-terminated polyurethane prepolymer with ethylenediamine, and adding glyoxal compound to react after the reaction is finished to obtain aldehyde-terminated pyridyl polyurethane APy-PU.
11. A hyperextension magnetic-responsive self-healing hydrogel prepared by the method of any one of claims 1-10.
12. The application of the hyperextension magnetic response self-repairing hydrogel of claim 11 in preparation of soft robots.
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