CN114933719A - Environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel and preparation method thereof - Google Patents

Environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel and preparation method thereof Download PDF

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CN114933719A
CN114933719A CN202210661673.6A CN202210661673A CN114933719A CN 114933719 A CN114933719 A CN 114933719A CN 202210661673 A CN202210661673 A CN 202210661673A CN 114933719 A CN114933719 A CN 114933719A
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hydrogel
zirconium ion
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tdn
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李学锋
陈晗予
许丹妮
黄以万
李倩
王紫云
沈佳琦
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Hubei University of Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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    • C08J2433/00—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
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Abstract

The invention provides the environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel and the preparation method thereof, which can obviously improve the adhesive property of the hydrogel, form strong adhesion with the surface of a substrate, and realize the cycle reversible process of strong adhesion and debonding by changing the environmental conditions. The preparation method provided by the invention comprises the following steps: step 1, stirring and dissolving poly 2-acrylamide-2-methyl sodium propanesulfonate (PNAAMPS), N-isopropylacrylamide (NIPAm), acrylamide (AAm), a cross-linking agent, an initiator and deionized water under a shading condition to obtain a uniform mixed solution, and carrying out ultraviolet polymerization to obtain PNAAMPS/P (NIPAM-co-AAm) double-network thermal sensitive hydrogel (TDN); and 2, putting the TDN obtained in the step 1 into a zirconium ion solution, then putting the TDN into a high-temperature deionized water solution, and obtaining the zirconium ion crosslinked thermal-sensitive hydrogel TDN-Zr with environment-responsive adhesion after swelling balance.

Description

Environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel and preparation method thereof
Technical Field
The invention belongs to the technical field of gel materials, and particularly relates to an environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel and a preparation method thereof.
Background
The hydrogel is a soft and wet material with wide application, has the characteristics of high deformability, structural similarity with biological tissues, large functional potential and the like, and is widely applied to the fields of tissue adhesives, wound dressings and the like. The surface of the traditional hydrogel material for the adhesive has a hydrated layer due to high water content, so that the adhesion effect of the traditional hydrogel material with the surface of a base material is prevented, the adhesion effect is poor, and the effective reversible adhesion effect is more difficult to realize, so that the designed hydrogel adhesive material with repeated reversible strong adhesion property has an application prospect in biomedical tissue adhesion gel.
Han et al [ Han L, Wang M, Prieto-Lopez L O, et al.Self-hydroionization in a dynamic hydrogel for creating nonpeptidic reusable apparatus addition [ J].Advanced Functional Materials,2020,30(7):1907064.]By Fe 3+ Inducing the formation of a dynamic self-hydrophobic surface, and preparing a dynamic hydrogel which can be repeatedly and stably adhered to various dry/wet matrixes underwater for a long time. The hydrogel with hydrophilic surface is soaked in the iron ion solution to induce the supermolecule functional groups to be rearranged on the surface, so that the hydrogel forms a hydrophobic surface, when the hydrogel is contacted with the surface of a matrix underwater, the hydrophobic functional groups can exclude water molecules on the surface of the substrate to realize sufficient contact, and the hydrogel can be rapidly and reversibly adhered underwater through hydrogen bonds, hydrophobic acting force and the like. But instead of the other end of the tubeSuch hydrogels do not have high adhesion strength and are difficult to achieve effective reversible adhesion to the surface of a dry substrate. Peng et al [ Pengziping, Zhuhekang, Yangyue, Wangji, Faqian ] preparation method of temperature-responsive adhesive injectable hydrogel [ P].CN108929412B,2020-10-23.]A preparation method of temperature-responsive adhesive injectable hydrogel is designed, wherein Dopamine Methacrylamide (DMA) is used as an adhesive monomer, and 2- (2-methoxyethoxy) ethyl Methacrylate (MEO) 2 MA) and oligo (ethylene glycol) methyl ether methacrylate (OEGMA) are used as temperature-sensitive monomers, temperature-responsive hydrogels with different dopamine contents are synthesized, and the prepared hydrogel can be applied to the fields of tissue adhesives and the like because the temperature-responsive adhesiveness is enhanced along with the increase of the temperature due to the adhesive strength of the hydrogel. But only the change in adhesion strength in a higher temperature environment is discussed and the adhesion strength is low. Therefore, the temperature-responsive adhesive hydrogel reported at present is difficult to realize high adhesive strength and effective reversible adhesion in a high-temperature environment in practical application.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a zirconium ion crosslinked thermosensitive hydrogel which is simple in process, easy to operate, easily available in raw materials, low in cost, and excellent in environmental responsiveness, and which is reversibly and strongly adherent, and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following scheme:
< method >
The invention provides a preparation method of an environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel, which is characterized by comprising the following steps:
step 1: stirring and dissolving poly (2-acrylamide-2-methyl propyl sulfonate) PNAAMPS, N-isopropyl acrylamide (NIPAm), acrylamide (AAm), a cross-linking agent, an initiator and deionized water under a shading condition to obtain a uniform mixed solution, and carrying out ultraviolet polymerization to obtain PNAAMPS/P (NIPAM-co-AAm) double-network thermal sensitive hydrogel (TDN);
step 2: and (2) putting the double-network thermal-sensitive hydrogel TDN obtained in the step (1) into a zirconium ion solution, then putting the double-network thermal-sensitive hydrogel TDN into a high-temperature deionized water solution, and obtaining the zirconium ion crosslinked thermal-sensitive hydrogel TDN-Zr with environmental-response adhesion after swelling balance.
Preferably, the preparation method of the environment-responsive adhesive zirconium ion-crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: in the step 1, dissolving 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium hydroxide (NaOH), a cross-linking agent and an initiator in deionized water, stirring the mixture in a dark place to obtain a uniform mixed solution, pouring the mixed solution into a parallel plate glass mold, carrying out ultraviolet photopolymerization to obtain poly (2-acrylamido-2-methylpropanesulfonic acid) sodium PNAAMPS hydrogel, drying the hydrogel in a vacuum drying oven to constant weight, grinding the hydrogel by using a high-speed ball mill, and sieving the ground hydrogel to obtain PNAAMPS microgel powder with the particle size of 10-200 mu m; wherein the concentration of AMPS is 3.98-4.02 mol L -1 (ii) a The concentration of NaOH solution is 1mol L -1 (ii) a The cross-linking agent is N, N' -methylene bisacrylamide MBAA, and accounts for 0.4 percent of the total molar amount of the monomers; the photoinitiator is 2-ketoglutaric acid KA, and accounts for 0.1 percent of the total mole amount of the monomers.
Preferably, the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: in the mixed liquid in the step 1, the NIPAm concentration is 3.48-3.52 mol L -1 The AAm concentration is 0.48-0.52 mol L -1 The cross-linking agent is N, N' -methylene bisacrylamide MBAA, and accounts for 0.1 percent of the total mole amount of the monomers; the photoinitiator is 2-ketoglutaric acid KA, and accounts for 0.01 percent of the total mole amount of the monomers.
Preferably, the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: in the step 1, the temperature during stirring is room temperature, and the stirring time is 30-40 min.
Preferably, the environmentally-responsive adhered zirconium ion-crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: in step 1, the conditions of illumination under an ultraviolet lamp are as follows: and (3) irradiating for 8-10 h under an ultraviolet lamp with the wavelength of 365nm and the power of 15W.
Preferably, the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: and (3) soaking the double-network thermal sensitive hydrogel TDN obtained in the step (1) in deionized water to remove unreacted monomers, and then entering the step (2).
Preferably, the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: in step 2, the concentration of the zirconium ion solution is 0.1-0.5 mol L -1 The time for soaking the zirconium ion solution is 24 hours.
Preferably, the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: in step 2, the high temperature is above 70 ℃, and the time for soaking in the high temperature deionized water is 48 hours.
< gel >
Further, the invention also provides the environment-responsive adhesive zirconium ion crosslinked thermal-sensitive hydrogel prepared by the method.
Preferably, the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel provided by the invention can also have the following characteristics: the zirconium ion crosslinked thermal-sensitive hydrogel TDN-Zr after being soaked in water at high temperature is fixed on the surface of the base material at room temperature to generate strong adhesion, can be separated from the surface of the base material after being soaked in water at room temperature, and can be strongly adhered to the base material again at room temperature after being soaked in water at high temperature, and the strong adhesion and separation processes can be repeated in an environment response cycle.
Preferably, in the above < method > and < gel >, the room temperature is 10 to 32 ℃, more preferably 25 to 30 ℃, and the high temperature is 70 to 90 ℃.
As shown in FIGS. 1 and 2, the environmentally-responsive adhesive zirconium ion crosslinked thermal hydrogel TDN-Zr prepared by the invention is obtained by soaking PNAAMPS/P (NIPAm-co-AAm) dual-network thermal hydrogel TDN in a zirconium ion solution. The NIPAm unit contains a hydrophilic amide group and a hydrophobic isopropyl group, and hydrophilic association and hydrophobic phase separation conversion of molecules in the hydrogel can be realized along with the change of the ambient temperature between room temperature and high temperature. Wherein zirconium ions with high ionization energy react with sulfonate-SO on PNAAMPS 3 - Group, P (NIPAm-co-AAm) carboxamide group-CONH 2 And the coordination with the imide group-CONH-group generates strong coordination synergy to form a special bonding network, and the coordination of zirconium ions can generate the functions of enhancing hydrophilicity and separating and fixing hydrophobic phase along with the change of the ambient temperature between room temperature and high temperature. When adhesion is needed, the hydrogel TDN-Zr is subjected to high-temperature water soaking treatment, the hydrophobic phase of the zirconium ion crosslinked thermosensitive hydrogel TDN-Zr is separated and arranged, the number of domains on the surface of the hydrogel is increased, so that the hydrophobic interaction binding sites on the surface of the hydrogel are increased and fixed by the zirconium ions, the self-hydrophobic effect is rapidly enhanced, the damage to a hydrated layer on the surface of the hydrogel is facilitated, and the strong interaction between interfaces is facilitated; the hydrogel is taken out and then is attached to the surface of a substrate (such as glass) at room temperature, the hydrogel can be tightly attached to the surface of the substrate, on one hand, chemical interactions such as hydrogen bonds, ionic bonds and the like are formed between the surface of the hydrogel and the surface of the substrate, on the other hand, the hydrogel is attached to a surface hardening layer of the substrate and an adhesive substrate to protect the water loss in the gel, the water in the hydrophobic association area of the gel surface contacted with the air is volatilized rapidly, the hydrogel surface is hardened, the relatively rough part of the surface of the base material (the surface of the base material has a plurality of convex-concave areas on the micro scale) is fixed in an attaching way, physical topological interlocking is formed between the hydrogel TDN-Zr and a substrate adhesion interface, so that the hydrogel TDN-Zr can be locked on the surface of the substrate, the chemical interaction and the physical interface topological interlocking are cooperated, the adhesive property of the hydrogel TDN-Zr is greatly improved, and effective strong adhesion is formed. When the adhesion is required to be removed, water is soaked at room temperature, due to the hydration of zirconium ions and the existence of hydrophilic associated areas in the hydrogel, the TDN-Zr of the hydrogel rapidly absorbs water and swells, the arrangement of the hydrophobic and hydrophilic associated areas is changed again, the number of the hydrophobic associated areas on the surface of the TDN-Zr of the hydrogel is rapidly reduced, the hydrophobic interaction binding sites are reduced, and the soft water film lubricating layer on the surface is formed again, so that the adhesion of the hydrogel from the surface of the base material is rapidly removed. When the hydrogel TDN-Zr needs to be adhered again, the hydrogel TDN-Zr is subjected to water soaking treatment at high temperature again, the surface of the hydrogel TDN-Zr shows hydrophobic characteristics again, hydrophobic and hydrophilic association areas are rearranged again, the hydrophobic combination sites on the surface are increased again, the hydrogel TDN-Zr is fixed on the surface of the base material again at room temperature, and the strength between the surface of the hydrogel TDN-Zr and the base material is highInteraction is formed again, stable interface topology interlocking is formed, and therefore the reversible process of the secondary strong adhesion circulation of temperature rise fixation is achieved. The strong adhesion and the adhesion removal processes can be performed in a reversible way in multiple cycles, and the reversible strong adhesion performance is stable and controllable.
The environment-responsive adhesive zirconium ion crosslinked thermal-sensitive hydrogel prepared by the invention has the advantages that the preparation process is simple and easy to control, the prepared hydrogel has uniform structure and stable performance, and zirconium ions and sulfonate-SO on PNAAMPS (polyacrylamide polymer electrolyte membrane) 3 - Group, P (NIPAm-co-AAm) carboxamide group-CONH 2 The special bonding network formed by strong coordination synergistic action with the imide group-CONH-group can promote the chemical interaction and physical topological interlocking between the surface of the hydrogel and the surface of the base material when adhesion is needed, so that the adhesion performance between the hydrogel and the base material is greatly improved to realize strong adhesion, when adhesion removal is needed, a hydrophilic association region existing in the hydrogel realizes adhesion removal through water absorption at room temperature, and the adhesion and adhesion removal process can be repeatedly carried out according to environmental changes as a controllable cyclic reversible process, which becomes a common method for preparing the environment-responsive adhesion composite material by using the metal ion crosslinked thermosensitive hydrogel.
Compared with the prior art, the invention has the following advantages and remarkable progress:
1) the invention has the advantages of simple preparation process, short production period, simple and convenient process conditions, easily obtained raw materials and low production cost.
2) According to the invention, the special bonding network formed by a zirconium ion crosslinking method is adopted, so that the adhesion performance of the hydrogel is obviously improved, strong adhesion is formed with the base material, the cyclic reversible process of strong adhesion and adhesion removal can be realized by changing the environmental conditions, and the hydrogel has a wide application prospect in the field of environment-responsive adhesive materials.
Drawings
FIG. 1 is a schematic diagram illustrating the preparation of an environmentally-responsive adhesive zirconium ion-crosslinked thermal hydrogel TDN-Zr according to the present invention; the tadpole-shaped structure is divided into two parts, wherein the front half part (comprising a head part and a half wave-shaped tail part) is light color and represents a hydrophilic group, and the back half part is dark color and represents an isopropyl hydrophobic group;
FIG. 2 is a schematic diagram showing the change of the network structure before and after soaking in water at a high temperature of TDN-Zr according to the present invention.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings.
Example 1
Step 1: 0.30g of PNAAMPS, 3.9606g of NIPAm (3.5mol L) were weighed out separately -1 )、0.3554g AAm(0.5mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the condition of shading to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal sensitive hydrogel TDN, balancing for 48h in deionized water, and removing unreacted monomers;
and 2, step: 0.1mol L of the preparation -1 Zirconium ion solution, adding the double-network thermal sensitive hydrogel TDN with balanced water soaking obtained in the step 1 into 0.1mol L -1 Soaking in a zirconium ion solution for 24 hours, then soaking in deionized water at 90 ℃ for 48 hours, and obtaining the zirconium ion crosslinked thermosensitive hydrogel TDN-Zr with environment-responsive adhesion through swelling balance.
Example 2
Step 1: 0.30g of PNAAMPS, 3.9493g of NIPAm (3.49mol L) were weighed out separately -1 )、0.3625g AAm(0.51mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the shading condition to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal sensitive hydrogel TDN, balancing for 48h in deionized water, and removing unreacted monomers;
step 2: 0.3mol L of the product is prepared -1 Zirconium ion solution, adding the double-network thermal sensitive hydrogel TDN with balanced water soaking obtained in the step 1 into 0.3mol L -1 Soaking in a zirconium ion solution for 24 hours, then soaking in deionized water at 90 ℃ for 48 hours, and obtaining the zirconium ion crosslinked thermosensitive hydrogel TDN-Zr with environment-responsive adhesion through swelling balance.
Example 3
Step 1: 0.30g of PNAAMPS, 3.9719g of NIPAm (3.51 m) were weighed out separatelyol L -1 )、0.3483g AAm(0.49mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the condition of shading to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal sensitive hydrogel TDN, balancing for 48h in deionized water, and removing unreacted monomers;
step 2: 0.5mol L of the product is prepared -1 Zirconium ion solution, adding the double-network thermal sensitive hydrogel TDN with balanced water soaking obtained in the step 1 into 0.5mol L -1 Soaking in the zirconium ion solution for 24 hours, then soaking in deionized water at 90 ℃ for 48 hours, and obtaining the zirconium ion crosslinked thermosensitive hydrogel TDN-Zr with environmental responsiveness adhesion through swelling balance.
Example 4
Step 1: 0.30g of PNAAMPS, 3.9606g of NIPAm (3.5mol L) were weighed out separately -1 )、0.3554g AAm(0.5mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the condition of shading to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal sensitive hydrogel TDN, balancing for 48h in deionized water, and removing unreacted monomers;
step 2: 0.3mol L of the product is prepared -1 Zirconium ion solution, adding the double-network thermal sensitive hydrogel TDN with balanced water soaking obtained in the step 1 into 0.3mol L -1 Soaking in zirconium ion solution for 24h, and soaking in deionized water at 70 deg.C for 48 h. Swelling and balancing to obtain the zirconium ion crosslinking thermosensitive hydrogel TDN-Zr with environment-responsive adhesion.
Example 5
Step 1: 0.30g of PNAAMPS, 3.9832g of NIPAm (3.52mol L) were weighed out separately -1 )、0.3412g AAm(0.48mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the condition of shading to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal sensitive hydrogel TDN, balancing for 48h in deionized water, and removing unreacted monomers;
and 2, step: 0.3mol L of the preparation -1 Zirconium ion solution, obtained by the step 1)Adding 0.3mol L of the obtained double-network thermo-sensitive hydrogel TDN with balanced soaking water -1 Soaking in zirconium ion solution for 24h, and soaking in 80 deg.C deionized water for 48 h. Swelling and balancing to obtain the zirconium ion crosslinking thermosensitive hydrogel TDN-Zr with environment-responsive adhesion.
Comparative example 1
Step 1: 0.30g of PNAAMPS, 3.9606g of NIPAm (3.5mol L) were weighed out separately -1 )、0.3554g AAm(0.5mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the condition of shading to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal-sensitive hydrogel TDN, soaking in deionized water at 90 ℃ for 48h, and swelling and balancing to obtain the thermal-sensitive hydrogel TDN.
Comparative example 2
Step 1: 0.30g of PNAAMPS, 3.9380g of NIPAm (3.48mol L) were weighed out separately -1 )、0.3696g AAm(0.52mol L -1 ) 0.0154g of MBAA (0.1 mol%), 0.0015g of KA (0.01 mol%) and 10mL of deionized water are stirred and dissolved under the condition of shading to obtain a uniform mixed solution; polymerizing for 8h under ultraviolet light irradiation to obtain PNAAMPS/P (NIPAm-co-AAm) double-network thermal sensitive hydrogel TDN, balancing for 48h in deionized water, and removing unreacted monomers;
step 2: 0.3mol L of the product is prepared -1 Zirconium ion solution, namely adding the double-network thermal sensitive hydrogel TDN with balanced bubble water obtained in the step 1 into 0.3mol L -1 Soaking in zirconium ion solution for 24h, then soaking in deionized water at 20 ℃ for 48h, and obtaining the zirconium ion crosslinked thermosensitive hydrogel TDN Zr after swelling balance.
And (3) adhesion performance test:
step 1: cutting the hydrogel sample strips soaked in deionized water for 24 hours at different temperatures into samples with the specification of 20mm in length and 15mm in width;
and 2, step: wiping off water on the surface of the sample obtained in the step (1), quickly adhering the sample between two smooth glass slides treated by an ultraviolet ozone cleaning machine at room temperature, constantly applying 16.67kPa pressure to an adhesion part by a 500g weight, and pressing for 10 min;
and 3, step 3: clamping by using universal mechanical testing machineTwo glass slides at both ends for 50mm min -1 The lap shear test is carried out on the adhesion sample between the hydrogel and the glass at the speed until the hydrogel is stripped, and a force-displacement curve is obtained.
And 4, step 4: soaking the hydrogel removed in the step 3 in deionized water at the same temperature for 24h, wiping off surface moisture, quickly adhering the hydrogel between two smooth glass slides treated by an ultraviolet ozone cleaning machine at room temperature, constantly applying 16.67kPa pressure to an adhesion part by a 500g weight, and pressing for 10 min;
and 5: clamping two ends of two glass slides by using a universal mechanical testing machine for 50mm min -1 The lapping shear test is carried out on the adhered sample between the hydrogel and the glass again at the speed of the second time until the hydrogel is removed from the adhesion for the second time, and a second force-displacement curve is obtained;
and 6: the sample adhesion strength L is calculated by adopting the ratio of the maximum force in the shearing process to the contact area of the sample and the glass substrate, and the calculation formula is as follows:
Figure BDA0003690772840000081
wherein F is the maximum shear force during stretching and is expressed in N; l is the overlapping length of the hydrogel sample and the glass substrate, and the unit is mm; b is the width in mm of the overlapping of the hydrogel sample and the glass substrate.
The adhesion strength of the zirconium ion-crosslinked thermosensitive hydrogel obtained in the above examples and comparative examples is shown in the following table 1:
table 1: adhesion strength of zirconium ion crosslinked thermosensitive hydrogel
Figure BDA0003690772840000082
Examples 1 to 3 are zirconium ion crosslinked thermosensitive hydrogels prepared by changing the concentration of a zirconium ion solution at an ambient temperature of 90 ℃, and examples 4 and 5 are those in which the concentration of a zirconium ion solution is 0.3mol L -1 In the case of (1) at 70 ℃ respectively,The zirconium ion crosslinked thermal-sensitive hydrogel TDN-Zr prepared at the temperature of 80 ℃, the comparative example 1 is the thermal-sensitive hydrogel TDN prepared without the zirconium ion crosslinking under the condition that the environmental temperature is 90 ℃, and the comparative example 2 is the zirconium ion solution with the concentration of 0.3mol L under the condition that the environmental temperature is 20 DEG C -1 And preparing the obtained zirconium ion crosslinked thermosensitive hydrogel TDN Zr.
According to the data in table 1:
as can be seen from examples 1 to 3, as the concentration of the zirconium ion solution increases, the adhesion strength of the zirconium ion crosslinked thermal hydrogel TDN-Zr with different concentrations increases firstly and then decreases at 90 ℃. Examples 2, 4 and 5 are examples in which the adhesion strength increases with increasing temperature under varying ambient temperatures. Compared with the examples 1 to 3, in the examples 1 to 3, the zirconium ions and the sulfonate groups of the first heavy PNAAMPS network and the amide and imide groups of the second heavy P (NIPAm-co-AAm) network in the thermosensitive hydrogel have strong ion coordination crosslinking effect, the volume of the hydrophobic association region taking the zirconium ions as the center is reduced at high temperature, the domains of the hydrophobic and hydrophilic association regions are uniformly distributed again, the number of the micro hydrophobic association regions distributed on the surface of the gel is gradually increased, so that the hydrophobic interaction binding sites on the surface of the hydrogel are increased, the hydrogel is adhered to the surface of a glass substrate at room temperature, the hydrophobic association regions taking the zirconium ions as the center are uniformly distributed on the surface of the hydrogel, the surface of the hydrogel rapidly loses water and hardens, meanwhile, the inside of the hydrogel keeps hydrophilic property, and the formation of the interaction such as hydrogen bonds and ionic bonds with the glass substrate with negative charges is facilitated, and macroscopic topological interlocking is formed on the surface of the substrate, so that the zirconium ion crosslinking obviously improves the adhesive strength of the thermosensitive hydrogel. In comparative example 2, after soaking in the zirconium ion solution, the soaking at 20 ℃ is carried out with water swelling balance, and the obtained TDN + Zr has extremely poor adhesion performance, while in examples 1 to 5, after soaking in the zirconium ion solution, the soaking at high temperature (70 ℃, 80 ℃ and 90 ℃) is carried out with water swelling balance, which shows that the self-hydrophobic effect of the hydrogel surface can be rapidly enhanced only after the swelling balance in a high-temperature environment, so that the adhesion performance between the zirconium ion crosslinked thermosensitive hydrogel TDN-Zr and the glass substrate is greatly improved at room temperature, the hydrogel surface not only forms chemical interactions such as hydrogen bonds, ionic bonds and the like with the substrate surface, but also becomes hardened by rapid dehydration of the hydrogel surface and forms physical topological interlocking with the substrate surface. The zirconium ion crosslinked thermal hydrogel in examples 1 to 5 was released from adhesion by soaking in water at room temperature, and then was fixed at room temperature by soaking in a high temperature environment again, so that secondary adhesion to the substrate was achieved and the adhesion strength was substantially consistent. And the strong adhesion and the adhesion removal can be repeatedly carried out, and the TDN-Zr shows excellent environment-responsive reversible strong adhesion performance.
The above embodiments are merely illustrative of the technical solutions of the present invention. The environmentally-responsive adhesive zirconium ion-crosslinked thermal hydrogel and the preparation method thereof according to the present invention are not limited to the contents described in the above embodiments, but are subject to the scope defined in the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (10)

1. The preparation method of the environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel is characterized by comprising the following steps of:
step 1: stirring and dissolving poly (2-acrylamide-2-methyl propyl sulfonate) PNAAMPS, N-isopropyl acrylamide (NIPAm), acrylamide (AAm), a cross-linking agent, an initiator and deionized water under a shading condition to obtain a uniform mixed solution, and carrying out ultraviolet polymerization to obtain PNAAMPS/P (NIPAM-co-AAm) double-network thermal sensitive hydrogel (TDN);
and 2, step: and (3) putting the double-network thermal-sensitive hydrogel TDN obtained in the step (1) into a zirconium ion solution, and then putting the double-network thermal-sensitive hydrogel TDN into a high-temperature deionized water solution, and obtaining the zirconium ion crosslinked thermal-sensitive hydrogel TDN-Zr with environment-responsive adhesion after swelling balance.
2. The method for preparing the environmentally-responsive adhesive zirconium ion-crosslinked thermosensitive hydrogel according to claim 1, wherein:
in the step 1, dissolving 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium hydroxide (NaOH), a cross-linking agent and an initiator in deionized water, stirring in the dark to obtain a uniform mixed solution, pouring the mixed solution into a parallel plate glass mold, carrying out ultraviolet polymerization to obtain poly (2-acrylamido-2-methylpropanesulfonic acid) sodium PNAAMPS hydrogel, drying the hydrogel in a vacuum drying oven to constant weight, grinding the hydrogel by using a high-speed ball mill, and sieving to obtain PNAAMPS microgel powder with the particle size of 10-200 mu m;
the concentration of AMPS is 3.98-4.02 mol L -1 (ii) a The concentration of NaOH solution is 1mol L -1 (ii) a The cross-linking agent is N, N' -methylene bisacrylamide MBAA, and accounts for 0.4 percent of the total molar amount of the monomers; the photoinitiator is 2-oxoglutarate KA, and accounts for 0.1 percent of the total mole amount of the monomers.
3. The method of preparing the environmentally-responsive, adherent, zirconium ion-crosslinked, thermally-sensitive hydrogel of claim 1, wherein:
wherein, in the mixed solution in the step 1, the NIPAm concentration is 3.48-3.52 mol L -1 The AAm concentration is 0.48-0.52 mol L -1 The cross-linking agent is N, N' -methylene bisacrylamide MBAA, and accounts for 0.1 percent of the total mole amount of the monomers; the photoinitiator is 2-ketoglutaric acid KA, and accounts for 0.01 percent of the total mole amount of the monomers.
4. The method of preparing the environmentally-responsive, adherent, zirconium ion-crosslinked, thermally-sensitive hydrogel of claim 1, wherein:
in the step 1, the temperature during stirring is room temperature, and the stirring time is 30-40 min.
5. The method of preparing the environmentally-responsive, adherent, zirconium ion-crosslinked, thermally-sensitive hydrogel of claim 1, wherein:
in step 1, the conditions of illumination under the ultraviolet lamp are as follows: and (3) irradiating for 8-10 h under an ultraviolet lamp with the wavelength of 365nm and the power of 15W.
6. The method of preparing the environmentally-responsive, adherent, zirconium ion-crosslinked, thermally-sensitive hydrogel of claim 1, wherein:
wherein, in the step 2, the concentration of the zirconium ion solution is 0.1-0.5 mol L -1 And the time for soaking the zirconium ion solution is 24 hours.
7. The method of preparing the environmentally-responsive, adherent, zirconium ion-crosslinked, thermally-sensitive hydrogel of claim 1, wherein:
in step 2, the high temperature is above 70 ℃, and the time for soaking in the high-temperature deionized water is 48 hours.
8. The environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel is characterized in that:
the preparation method of the environment-responsive adhesion zirconium ion crosslinked thermosensitive hydrogel according to any one of claims 1 to 7.
9. The environmentally-responsive, adherent, zirconium ion-crosslinked, thermally-sensitive hydrogel of claim 8, wherein:
the zirconium ion crosslinked thermal-sensitive hydrogel TDN-Zr after being soaked in water at high temperature is fixed on the surface of the base material at room temperature to generate strong adhesion, can be separated from the surface of the base material after being soaked in water at room temperature, and can be strongly adhered to the base material again at room temperature after being soaked in water at high temperature, and the strong adhesion and separation processes can be repeated in an environment response cycle.
10. The method for producing the environmentally-responsive adhesive zirconium ion-crosslinked thermosensitive hydrogel according to any one of claims 1 to 7 or the environmentally-responsive adhesive zirconium ion-crosslinked thermosensitive hydrogel according to claim 9, wherein:
wherein the room temperature is 10-32 ℃, and the high temperature is 70-90 ℃.
CN202210661673.6A 2022-06-13 2022-06-13 Environment-responsive adhesive zirconium ion crosslinked thermosensitive hydrogel and preparation method thereof Pending CN114933719A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114354554A (en) * 2021-12-17 2022-04-15 北京科技大学 Preparation method and application of detection platform for full-time line biomarker

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114354554A (en) * 2021-12-17 2022-04-15 北京科技大学 Preparation method and application of detection platform for full-time line biomarker
CN114354554B (en) * 2021-12-17 2023-12-26 北京科技大学 Preparation method and application of detection platform for full-time line biomarker

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