CN110591122A - Antistatic self-recovery triple interpenetrating network silicon hydrogel and preparation method thereof - Google Patents

Antistatic self-recovery triple interpenetrating network silicon hydrogel and preparation method thereof Download PDF

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CN110591122A
CN110591122A CN201911046393.9A CN201911046393A CN110591122A CN 110591122 A CN110591122 A CN 110591122A CN 201911046393 A CN201911046393 A CN 201911046393A CN 110591122 A CN110591122 A CN 110591122A
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network
hydrogel
silicon
monomer
silicone hydrogel
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CN110591122B (en
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杨倩玉
高晨
张雪梅
赵星宇
郑晓翼
邹智挥
钟家春
夏益青
盛玉萍
袁力
曾春燕
白兰涵
附怡清
杨婷
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Sichuan University of Science and Engineering
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • 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
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Abstract

The invention discloses an antistatic self-recovery triple interpenetrating network silicone hydrogel and a preparation method thereof, wherein the preparation method comprises the steps of forming a carbon chain polymer by addition polymerization of vinyl monomers, forming a first high molecular network by hydrophobic association crosslinking of the carbon chain polymer, forming a silicon-containing polymer by condensation polymerization of silicon monomers, forming a second high molecular network by the silicon-containing polymer through a hydrogen bond function, forming polyaniline by oxidative polymerization of aniline monomers, and forming a third high molecular network by the polyaniline through a hydrogen bond or a hydrogen bond/covalent crosslinking function; the first polymer network, the second polymer network and the third polymer network are interpenetrating. The silicon hydrogel obtained by the invention has excellent toughness, quick self-recovery performance and antistatic performance. The preparation process is simple, the raw materials are simple and easy to obtain, the preparation cost is low, the industrial production is facilitated, and the application prospect is good.

Description

Antistatic self-recovery triple interpenetrating network silicon hydrogel and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogel composite modification, and particularly relates to an antistatic self-recovery triple interpenetrating network silicon hydrogel and a preparation method thereof.
Background
The hydrogel has a plurality of similarities with organism soft tissues, so the hydrogel has wide application prospects in the aspects of life science, food science, drug controlled release, biosensors, tissue engineering and the like. However, the traditional hydrogel has poor mechanical properties, the tensile strength is only about 10 kPa, and the breaking energy is only 170kJ/m3On the other hand, the micro cracks generated by the damage of the liquid erosion or the extrusion by external force during the use process gradually expand and propagateThe integrity of the hydrogel is destroyed and the destruction is usually irreversible and difficult to repair, which severely limits its practical application.
In recent years, researchers have improved the mechanical properties of hydrogels through various structural designs, such as double-network hydrogels, slip-ring hydrogels, polymer microsphere hydrogels, organic/inorganic composite hydrogels, hydrophobically-associated hydrogels, and the like. The double-network hydrogel is formed by mutually inserting two high-molecular networks, so that energy can be effectively dissipated, and the mechanical property of the hydrogel is remarkably improved. The double-network hydrogel developed in the early stage is formed by mutually inserting two covalent bond cross-linked networks, and although the mechanical property of the hydrogel can be effectively improved, the chemically cross-linked double-network hydrogel does not have good fatigue resistance and self-recovery performance due to the irreversibility of chemical cross-linking. Therefore, the self-repairing hydrogel can self-repair microcracks generated by the self-repairing hydrogel, and has attracted much attention of researchers at home and abroad in recent years. For example, the invention patent CN201811375210.3 discloses a carboxyethyl chitosan/polyvinyl alcohol self-healing hydrogel, and a preparation method and an application thereof, the hydrogel takes carboxyethyl chitosan as a matrix, and is blended with polyvinyl alcohol and then crosslinked by adopting an oxidized sodium alginate-boric acid composite crosslinking system, so that a novel multiple crosslinking network structure is constructed, but the hydrogel structure provided by the invention is a single polymer network with multiple crosslinking functions, and mutual suppression exists among different crosslinking functions in the same network, so that the self-healing performance of the hydrogel is limited to a certain extent. The invention patent CN201810840345.6 discloses a preparation method of a PAA (polyacrylic acid) double-crosslinked network self-healing hydrogel capacitive pressure sensor, which comprises the steps of firstly taking acrylic acid and acrylamide as base materials, adding iron ions to form coordination ion crosslinking, and forming a physical and chemical hybridization double-layer crosslinking three-dimensional network structure, wherein the obtained hydrogel not only has strong mechanical properties, but also has the characteristic of rapid self-healing. However, the hydrogel provided by the invention is a single network structure of physical-chemical hybrid double cross-linking, mutual containment exists among different cross-linking actions in the same network, the self-recovery performance of the hydrogel is limited to a certain extent, and the chemical covalent cross-linking has the characteristics of non-reversibility and non-uniform cross-linking action, so that the mechanical performance, the fatigue resistance and the self-recovery performance of the hydrogel are limited. The invention patent CN201810342852.7 discloses a preparation method of self-healing hydrogel with ultraviolet and pH sensitivity, which comprises the following steps: step 1, preparing an azobenzene polymerizable monomer, and forming a host-guest inclusion compound by using cyclodextrin and the azobenzene polymerizable monomer; step 2, preparing a phenylboronic acid polymerizable monomer; step 3, reacting a phenylboronic acid polymerizable monomer with cis-diol on the cyclodextrin inclusion compound under an alkaline condition to form a crosslinking point, separating liquid by using a separating funnel, wherein the yellow emulsion at the lowermost layer is the formed azobenzene cyclodextrin inclusion compound; step 4, adding a redox initiator, a cross-linking agent and a water-soluble monomer at room temperature to obtain hydrogel with ultraviolet and pH responsiveness and self-healing performance; adopts simple synthesis steps, depends on a physical non-covalent host-guest package and action and a chemical covalent reversible boric acid ester bond, and forms the hydrogel with self-healing function, pH sensitivity, strong mechanical property and stability. However, in the preparation process provided by the invention, an azobenzene polymerizable monomer and a phenylboronic acid polymerizable monomer are respectively synthesized in advance, then the cyclodextrin aqueous solution and the azobenzene polymerizable monomer are mixed and separated, and finally the separated mixed solution, the phenylboronic acid polymerizable monomer, the acrylamide monomer, the initiator and the crosslinking agent are uniformly mixed and polymerized into gel. The preparation process is complex and the process cost is high. Patent CN108822561A discloses a silicon rubber material of self-repairing type, sets up the mounting groove in the silicon rubber body, is fixed with X type connecting material body at the top and the bottom of mounting groove inner wall, is fixed with the self-repairing elastic fibrous body in one side that the silicon rubber was kept away from to X type connecting material body, obtains the silicon rubber that has good self-recovery performance. However, the proposed method can only realize the self-repairing performance of a specific position, the self-repairing performance of the whole material is not uniform, the operation process is complex, and the technical requirement is high.
Although the mechanical strength, ductility, self-healing property and the like of the hydrogel are remarkably improved, the multifunctional research on the hydrogel is a hot spot at present. The silicon-containing polymer has excellent structural designability and performance adjustability, and is widely applied to the fields of medical treatment and health, electronic information, automobile machinery, daily life and the like. However, the silicon-containing polymer has good insulation, so that static electricity is easy to accumulate in the use process, and dust is adsorbed, and discharge and potential safety hazards are caused. Therefore, the improvement of the antistatic performance of the silicon-containing polymer has important significance for improving the comprehensive performance and the application value of the silicon-containing polymer. For example, patent CN201910472178.9 proposes a method for preparing antistatic silicone rubber, which can reduce the volume resistivity of silicone rubber to 1.73 × 106 Ω · cm by adding composite antistatic agent, but the formula of the composite antistatic agent uses nano copper powder and superconducting carbon black, so to make the antistatic agent in silicone rubber uniformly distributed without aggregation, it needs to adopt a more complicated process: open milling, filtering and five-section hot drying treatment increase the equipment cost and the complexity of the process. The traditional silicon-containing elastomer adopts a vulcanization covalent crosslinking method to form a chemical network structure so as to obtain high elasticity. However, once the chemical covalent bond is broken, it cannot be spontaneously reconstructed, resulting in a reduction in mechanical properties of the material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an antistatic self-recovery triple interpenetrating network silicon hydrogel, which solves the problems that the existing silicon hydrogel cannot simultaneously have good mechanical property, fatigue resistance, self-recovery property and antistatic property and silicon-containing polymer is easy to accumulate static electricity.
The invention also provides a preparation method of the antistatic self-recovery triple interpenetrating network silicone hydrogel, and solves the problem that the preparation process of the existing method is complex.
In order to achieve the purpose, the invention adopts the following technical scheme: an antistatic self-recovery triple interpenetrating network silicone hydrogel comprises a carbon chain polymer formed by addition polymerization of vinyl monomers, wherein the carbon chain polymer is crosslinked to form a first high molecular network through hydrophobic association; forming a silicon-containing polymer by condensation polymerization of a silicon monomer, wherein the silicon-containing polymer forms a second polymer network through hydrogen bonding; polyaniline is formed by oxidizing and polymerizing aniline monomers, and a third polymer network is formed by the polyaniline through hydrogen bonds or hydrogen bond/covalent crosslinking; the first polymer network, the second polymer network and the third polymer network are interpenetrating.
Preferably, the vinyl monomers include hydrophobic vinyl monomers and hydrophilic vinyl monomers, and the hydrophilic vinyl monomers carry at least one anion; the silicon monomer is one or more of hexamethyldisiloxane, ethyl orthosilicate and methyltrimethoxysilane; the aniline monomer is aniline or an aniline derivative.
Therefore, the first polymer network is a carbon chain polymer network formed by vinyl monomers and comprises hydrophilic vinyl monomers and hydrophobic vinyl monomers, the molar ratio of the hydrophilic vinyl monomers to the hydrophobic vinyl monomers can be adjusted at will to regulate and control the hydrophilic-hydrophobic property and the hydrophobic association crosslinking density of the first polymer network, and the hydrophilic vinyl monomers can also comprise monomers (such as acrylic acid or methacrylic acid) carrying anions, so that a structural basis is provided for obtaining the ion-reinforced hydrogel through ion coordination crosslinking.
The second polymer network is an element organic polymer network formed by silicon-containing monomers and can be formed by condensation polymerization of a plurality of silicon-containing monomers with different functionalities, wherein the molar ratio of the silicon-containing monomers with different functionalities can be adjusted at will, and a wider space is provided for designing the second polymer networks with different organic-inorganic structure ratios and different space topological structures.
The third polymer network is a heterochain conductive polymer network formed by oxidizing and polymerizing aniline monomers, the molar ratio of the monomers to the cross-linking agent can be adjusted at will, so that the cross-linking density can be flexibly designed and adjusted, cross-linking can be carried out in a hydrogen bond or hydrogen bond/covalent compound mode, the relative content of different cross-linking modes can be adjusted at will, and the structure of the third polymer network and the comprehensive performance of the hydrogel can be flexibly adjusted.
Preferably, the hydrophobic vinyl monomer is octadecyl methacrylate and/or hexadecyl methacrylate; the hydrophilic vinyl monomer is one or more of acrylamide, methacrylamide, acrylic acid and methacrylic acid.
The preparation method of the antistatic self-recovery triple interpenetrating network silicone hydrogel comprises the following steps:
1) dissolving an alkene monomer, an emulsifier and an initiator in deionized water, adding a silicon-containing monomer, a catalyst and a cosolvent, uniformly stirring to obtain a mixed solution, adding the mixed solution into a glass mold, carrying out polymerization reaction at the temperature of 60 ℃ and ~ 80 ℃ for 20h and ~ 28h, and after the polymerization reaction is finished, putting the obtained hydrogel in deionized water for dialysis to obtain double-network silicon hydrogel;
2) immersing the double-network silicon hydrogel obtained in the step 1) into an aqueous solution containing aniline monomers and a cross-linking agent, taking out the double-network silicon hydrogel, immersing the double-network silicon hydrogel into an aqueous solution of an oxidant for oxidative polymerization, and immersing the double-network silicon hydrogel into deionized water for 24 ~ 36 hours after the polymerization reaction is finished, thereby obtaining the triple interpenetrating network silicon hydrogel.
Preferably, the step 2) further comprises immersing in an aqueous solution of iron ions after the oxidative polymerization, wherein the concentration of the iron ions is 0.05 ~ 0.2.2 mol/L, and the immersion time is 24 ~ 36 h.
Therefore, iron ions can be effectively combined with anions in polyacrylic acid polymer chains in the hydrogel through ion coordination to form an ion network to be inserted into the hydrogel network, and the strength and the toughness of the hydrogel can be effectively improved.
Preferably, the emulsifier in the step 1) is cetyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride, the initiator is potassium persulfate or ammonium persulfate, the mass ratio of the emulsifier to the vinyl monomer is 0.4 ~ 0.48.48: 1, and the mass ratio of the initiator to the vinyl monomer is 0.001 ~ 0.006.006: 1.
Preferably, the total monomer concentration in the mixed solution in the step 1) is 2.5 ~ 3.0.0 mol/L, and the mass ratio of the vinyl monomer to the silicon-containing monomer is 1.0 ~ 1.3.3: 1.
Preferably, the catalyst in the step 1) is concentrated hydrochloric acid, the mass ratio of the catalyst to the silicon-containing monomer is 0.6 ~ 1.0.0: 1, the cosolvent is ethanol, and the mass ratio of the cosolvent to the silicon-containing monomer is 0.3 ~ 0.6.6: 1.
Preferably, the concentration of the aniline monomer in the mixed aqueous solution in the step 2) is 0.14 ~ 0.18.18 g/mL, the crosslinking agent is phytic acid and/or p-phenylenediamine, the mass ratio of the crosslinking agent to the aniline monomer is 2.3 ~ 2.7.7: 1, and the mass ratio of the aniline monomer to the alkene monomer is 0.15 ~ 0.25.0.25: 1.
Preferably, the oxidant in the step 2) is ammonium persulfate or potassium persulfate, and the aqueous oxidant solution is 2.2 ~ 2.8.8 mol/L.
Preferably, the temperature of the mixed aqueous solution containing aniline monomer and cross-linking agent in the step 2) is 2 ~ 8 ℃, the immersion time of the double-network silicon hydrogel is 10 ~ 14 hours, the temperature of the oxidant aqueous solution is 2 ~ 8 ℃, and the immersion time of the double-network silicon hydrogel is 10 ~ 14 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. in the triple interpenetrating network hydrogel prepared by the invention, the first polymer network is a flexible hydrophobic association crosslinking network, and the hydrogel has good antistatic performance due to the fact that the hydrogel contains anions; the second polymer network is a rigid hydrogen bond crosslinking network, and the mechanical property of the hydrogel is improved by the inorganic structural component with alternate Si-O bonds; the third polymer network is a hydrogen bond or a hydrogen bond/covalent crosslinking network, and the polyaniline structure in the network improves the conductivity of the hydrogel. The reversible physical crosslinking in the three networks provides the hydrogel with excellent fatigue resistance and self-recovery performance, wherein HPAMAA-Si3MQThe PANI hydrogel is subjected to five times of cyclic stretching under 200% strain, is subjected to cyclic stretching under 200% strain after being placed for 5min at room temperature, recovers 122% of strength and 93.5% of toughness, recovers 133% of strength and 97.2% of toughness when being placed for 10min at room temperature, and shows excellent self-recovery performance, and the surface resistance of the hydrogel is 105Omega, has excellent antistatic performance. The chemical structures and the crosslinking densities in different networks can be freely designed, a wider space is provided for constructing the hydrogel with excellent comprehensive performance, and the hydrogel has good application prospects in the fields of biomedicine, environmental protection, electronic information and the like.
2. In the preparation method of the antistatic self-recovery triple interpenetrating network silicone hydrogel, two macromolecular networks with different structures and mutually interpenetrated are formed by a one-pot method, wherein two network monomers are polymerized under the same process condition through free radical addition polymerization and condensation polymerization respectively, and the polymerization processes are not interfered with each other. And then the double-network silicon hydrogel is sequentially immersed in an aniline monomer and oxidant solution to form a third polymer network through an oxidation method, heating or ultraviolet illumination is not needed in the process, the operation is simple, the raw materials are simple and easy to obtain, the preparation cost is low, the industrial production is facilitated, and the application prospect is good.
3. In the triple interpenetrating network structure designed by the invention, the third polymer network can carry out chemical crosslinking on the polyaniline polymer chain by adding p-phenylenediamine besides the polyaniline polymer chain, and the tensile strength and the modulus of the hydrogel are obviously improved because the crosslinking point contains a rigid group benzene ring; and through adding the p-phenylenediamine/phytic acid composite cross-linking agent, the polyaniline third polymer network can be cross-linked in a covalent bond and hydrogen bond double cross-linking mode, rigid chemical cross-linking effect and flexible physical hydrogen bond cross-linking effect are matched in a synergistic mode, rigidity and flexibility can be effectively achieved, and the mechanical strength, toughness and self-recovery performance of the hydrogel are synergistically improved.
4. The antistatic self-recovery triple interpenetrating network silicone hydrogel provided by the invention can realize the compatibility of molecular size by mutually interpenetration of a polyaniline high-molecular network (conductive polymer network) and/or an ion-containing network and a silicon-containing high-molecular network, and simultaneously avoids the static accumulation effect of the silicon-containing polymer, thereby realizing the antistatic effect of the hydrogel. The invention does not need to use inorganic antistatic filler and complex blending process, and has simple process and lasting and stable antistatic performance.
5. The silicon hydrogel elastomer provided by the invention has rapid and good self-recovery performance, and the principle is realized by reconstructing physical actions such as macromolecular inter-chain hydrogen bonds, hydrophobic association, chain entanglement and the like, so that the silicon hydrogel material has uniform self-recovery performance, is not limited to self-repair of local positions, does not need to assemble additional structural components such as self-repair fiber bodies and the like in a material body, and has simple process and low cost.
Drawings
FIG. 1 shows a silicone hydrogel HPAMAA-Si prepared in example 1 of the present invention3MQ-a five cycle tensile curve of PANi at 200% strain;
FIG. 2 shows a silicone hydrogel HPAMAA-Si prepared in example 1 of the present invention3MQ-a cyclic stretch curve of 5min and 10min for recovery of PANi after five cyclic stretches at 200% strain;
FIG. 3 shows a silicone hydrogel HPAMAA-Si prepared in example 2 of the present invention3MQ-a five cycle tensile curve of PANi/PPDA at 200% strain;
FIG. 4 shows a silicone hydrogel HPAMAA-Si prepared in example 2 of the present invention3MQ-cyclic stretch curve at 5min recovery after five cyclic stretches of PANi/PPDA at 200% strain;
FIG. 5 shows a silicone hydrogel HPAMAA-Si prepared in example 2 of the present invention3MQCyclic tensile curves of PANi/PPDA at different strains;
FIG. 6 shows a silicone hydrogel HPAMAA-Si prepared in example 3 of the present invention3MQ-PANi/PPDA-0.1FeCl3Cyclic tensile curve at 50% strain.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings, and the following experimental methods are not specifically described as conventional methods.
Tenacity recovery for continuous drawingRCalculated using equation 1:
formula 1
In the formula 1, the reaction mixture is,S ci represents the integral area of the stretch-retraction loop in the ith cycle of stretching of the hydrogel,S c1 represents the integrated area of the stretch-retraction loop in the first cycle of stretching of the hydrogel.
Example 1:
a preparation method of antistatic self-recovery triple interpenetrating network silicone hydrogel comprises the following steps:
1) adding 24mL of deionized water into a 100mL beaker, adding 3.75g of acrylamide AM, 0.47g of acrylic acid AA, 2g of hexadecyl trimethyl ammonium bromide and 0.31g of octadecyl methacrylate, stirring at a certain temperature to dissolve the acrylamide, adding 2mL of ethanol, 1g of hexamethyldisiloxane, 3.25g of ethyl orthosilicate and 3mL of concentrated hydrochloric acid after stirring uniformly, and continuing to stir. Dissolving 20mg of potassium persulfate in 1mL of deionized water, adding the solution into the solution, transferring the prepared solution into a self-made glass mold, and polymerizing the solution at 70 ℃ for 24 hours to obtain the double-network silicon hydrogel HPAMAA-Si3MQDumbbell bars (3 stands for the amount of hydrochloric acid added, M and Q for hexamethyldisiloxane and ethyl orthosilicate, respectively).
2) Preparing 4mL of 50% phytic acid aqueous solution, 920 mu L of aniline and 2mL of deionized water into aniline/phytic acid solution, and then preparing HPAMAA-Si3MQSoaking the hydrogel dumbbell-shaped sample bar in aniline/phytic acid solution at 4 ℃ for 12h, taking out the sample bar, soaking the sample bar in ammonium persulfate solution at 4 ℃ (taking 3.51g of ammonium persulfate and 6mL of deionized water) for 12h, taking out the sample bar, and soaking the sample bar in deionized water for 12h to obtain the triple interpenetrating network silicon hydrogel HPAMAA-Si3MQ-PANi。
1. Testing of HPAMAA-Si by surface resistivity instrument3MQThe surface resistance of the-PANI hydrogel was 105Omega, illustrating the HPAMAA-Si prepared in this example3MQThe PANI hydrogel has good antistatic performance.
2. HPAMAA-Si prepared in this example3MQthe-PANI hydrogel is subjected to a fatigue resistance test, and a stress-strain curve of five-cycle stretching under 200% strain according to the national standard GB/T1040.2-2006 is shown in FIG. 1.
As can be seen from the figure, the hydrogels prepared in this example have an internal energy consumption of 0.108MJ/m in the first to fifth cycle stretching3、 0.060MJ/m3、0.055MJ/m3、0.051MJ/m3And 0.048MJ/m3。HPAMAA-Si3MQ-second pass of PANI hydrogelThe toughness recoveries up to the fifth time were 55.6%, 50.9%, 47.2%, and 44.4%, respectively. The method shows good toughness recovery efficiency and shows the characteristic that the physical cross-linking of hydrogen bonds has quick reconstruction. HPAMAA-Si3MQThe residual strains of the PANi hydrogel at the first to fifth cycle tensile unloading were 110.0%, 122.7%, 131.5%, 136.5% and 140.5%, respectively, compared to HPAMAA-Si in example 23MQthe-PANI/PPDA hydrogel had less residual strain than the-PANi/PPDA hydrogel, because of the low strain at HPAMAA-Si3MQWhen the PANI hydrogel is stretched, the broken third network hydrogen bond crosslinking points of the PANI can be rapidly reconstructed, and HPAMAA-Si3MQWhen the PANI/PPDA hydrogel is stretched, covalent crosslinking points in a third network of the PANI restrict the movement of a macromolecular chain, and the reconstruction of hydrogen bond crosslinking points is hindered to a certain extent. Data for residual strain indicate HPAMAA-Si3MQThe PANI hydrogel has more excellent self-recovery performance. The physical cross-linking of the single hydrogen bonds in the third polymer network is demonstrated to have the property of being rapidly reestablished after being destroyed. HPAMAA-Si3MQThe residual strain of the PANi hydrogel at the first 200% cyclic stretching unloading was 110.0%, and at the beginning of the immediately second 200% cyclic stretching, the residual strain had decreased to 48.0% (obtained by calculating the intersection of the tangent line with the maximum slope at the beginning of the second cyclic stretching with the x-axis). Similarly, the second cycle unloaded residual strain to 122.7%, with the residual strain decreasing to 57.0% at the beginning of the next third cycle of stretching; the third cycle unloaded residual strain to 131.5%, with a 60.3% reduction in residual strain at the beginning of the next fourth cycle of stretching; the fourth cycle unloaded the residual strain to 136.5%, with the residual strain decreasing to 66.3% at the beginning of the next fifth cycle of stretching. The residual strain data further demonstrate HPAMAA-Si in a short time3MQThe PANI hydrogel has rapid self-recovery performance.
3. Mixing HPAMAA-Si3MQThe cyclic extension curves of the PANi hydrogel at different recovery times are shown in fig. 2.
As can be seen, HPAMAA-Si was obtained after 5 cycles of stretching3MQThe PANI hydrogel was left at room temperature for 5min and then subjected to a 200% strain cycle stretch again, the most soThe large stress is 0.11MPa, which is 122 percent of the original sample bar (0.09 MPa), and the internal energy consumption is 0.101MJ/m3The toughness was recovered by 93.5%. Standing for 10min, and performing 200% strain cyclic stretching to obtain the final product with maximum stress of 0.12MPa (133% of original sample bar (0.09 MPa) and internal energy consumption of 0.105MJ/m3The toughness was recovered by 97.2%. Tensile test shows HPAMAA-Si3MQThe PANI hydrogel has excellent fatigue resistance and self-recovery performance, can still maintain good toughness after 5 times of 200% cyclic stretching, and can recover 93.5% of toughness and 122% of stress only within 5min, and the stress exceeds the original sample strip because the polymer chains in the hydrogel sample strip are oriented in the stretching direction after the hydrogel sample strip is subjected to multiple cyclic stretching, so that the stress which can be borne in the axial direction of the hydrogel dumbbell-shaped sample strip is increased.
Example 2:
a preparation method of antistatic self-recovery triple interpenetrating network silicone hydrogel comprises the following steps:
1) a100 mL beaker was charged with 24mL of deionized water, 3.75g of acrylamide AM, 0.47g of acrylic acid AA, 2g of cetyltrimethylammonium bromide and 0.31g of stearyl methacrylate, and dissolved by stirring at a certain temperature. After stirring uniformly, 2mL of ethanol, 1g of hexamethyldisiloxane, 3.25g of ethyl orthosilicate and 3mL of concentrated hydrochloric acid are added in sequence, and stirring is continued. 20mg of potassium persulfate was dissolved in 1mL of deionized water and added to the above solution. Transferring the prepared solution into a self-made glass mold, and polymerizing for 24 hours at 70 ℃ to obtain the double-network silicon hydrogel HPAMAA-Si3MQDumbbell bars (3 stands for the amount of hydrochloric acid added, M and Q for hexamethyldisiloxane and ethyl orthosilicate, respectively).
2) Taking 4mL of 50% phytic acid aqueous solution, 920 mu L of aniline solution, 22mg of p-phenylenediamine and 2mL of deionized water to prepare p-phenylenediamine/aniline/phytic acid solution. Then the HPAMAA-Si prepared in the step 1) is added3MQSoaking dumbbell-shaped sample bars in phenylenediamine/aniline/phytic acid solution for 12h at 4 ℃, taking out the sample bars, soaking the sample bars in ammonium persulfate solution (taking 3.51g of ammonium persulfate and 6mL of deionized water) at 4 ℃ for 12h, and finally soaking the sample bars in the ammonium persulfate solution (taking 3.51g of ammonium persulfate and 6mL of deionized water)Taking out the sample strips, and soaking in deionized water for 12h to obtain the triple interpenetrating network silicon hydrogel HPAMAA-Si3MQ-PANi/PPDA。
1. Testing of HPAMAA-Si by surface resistivity instrument3MQThe surface resistance of the-PANI/PPDA hydrogel was 106Omega, which shows that the hydrogel prepared in this example has good antistatic property.
2. HPAMAA-Si prepared in this example3MQThe fatigue resistance of the-PANI/PPDA hydrogel was tested, and the stress-strain curve of the tensile test was shown in FIG. 3 according to the national standard GB/T1040.2-2006, with five cycles of tensile at 200% strain.
As can be seen from the figure, the internal energy consumptions of the first to fifth cycles of stretching are 0.241MJ/m3、 0.100MJ/m3、0.085MJ/m3、0.077 MJ/m3And 0.070 MJ/m3。HPAMAA-Si3MQThe toughness recovery rates of the-PANI/PPDA hydrogel from the second time to the fifth time are 41.5%, 35.3%, 32.0% and 29.0%, respectively, and good toughness recovery efficiency is shown. HPAMAA-Si3MQThe residual strain at the first to fifth cycle tensile unloading of the PANi/PPDA hydrogel was 160.1%, 166.2%, 168.8%, 171.4% and 171.6%, respectively. HPAMAA-Si3MQThe residual strain of the PANi/PPDA hydrogel at the beginning of the stretching of the immediately second to fifth cycles had been reduced to 88.6%, 95.5%, 101.7% and 107.6%, respectively. Data on residual strain also demonstrate HPAMAA-Si3MQThe PANI/PPDA hydrogel has good self-recovery performance.
3. The cyclic elongation curve of 200% strain taken once more after 5 cycles of elongation followed by 5min of room temperature recovery is shown in FIG. 4.
The result shows that after the room temperature is recovered for 5min, the internal energy consumption is 0.124MJ/m3The toughness is recovered by 51.5 percent, and the good self-recovery performance is shown.
4. Mixing HPAMAA-Si3MQ-PANI/PPDA hydrogel successively at 50%, 100%, 150% and 200% strain to HPAMAA-Si3MQThe PANI/PPDA hydrogel was subjected to a cyclic tensile test, and the stress-strain curve is shown in FIG. 5.
As can be seen from the figure, HPAMAA-Si3MQThe internal energy consumptions of the PANi/PPDA hydrogel in cyclic extension at 50%, 100%, 150% and 200% strain were 0.043 MJ/m, respectively3、0.085 MJ/m3、0.110 MJ/m3、0.135 MJ/m3As the strain increases, the internal power consumption also increases gradually. HPAMAA-Si3MQThe residual strains of the-PANI/PPDA hydrogel after 50%, 100%, 150% and 200% strain cycling stretching were 41.5%, 80.3%, 113.5% and 144.2%, respectively. And the tensile curve at each subsequent higher strain always crosses the hysteresis loop stretched in the previous cycle, indicating HPAMAA-Si3MQCertain rapid toughness recovery capability of-PANI/PPDA hydrogel, and the cyclic tensile test proves that HPAMAA-Si3MQThe PANi/PPDA hydrogel has excellent fatigue resistance and self-recovery performance.
Example 3:
a preparation method of antistatic self-recovery triple interpenetrating network silicone hydrogel comprises the following steps:
1) a100 mL beaker was charged with 24mL of deionized water, 3.75g of acrylamide AM, 0.47g of acrylic acid AA, 2g of cetyltrimethylammonium bromide and 0.31g of stearyl methacrylate, and dissolved by stirring at a certain temperature. After stirring uniformly, 2mL of ethanol, 1g of hexamethyldisiloxane, 3.25g of ethyl orthosilicate and 3mL of concentrated hydrochloric acid are added in sequence, and stirring is continued. 20mg of potassium persulfate was dissolved in 1mL of deionized water and added to the above solution. Transferring the prepared solution into a self-made glass mold, and polymerizing for 24h at 70 ℃ to obtain the hydrophobic silica hydrogel HPAMAA-Si3MQDumbbell bars (3 stands for the amount of hydrochloric acid added, M and Q for hexamethyldisiloxane and ethyl orthosilicate, respectively).
2) Taking 4mL of 50% phytic acid aqueous solution, 920 mu L of aniline solution, 22mg of p-phenylenediamine and 2mL of deionized water to prepare p-phenylenediamine/aniline/phytic acid solution. Then adding HPAMAA-Si3MQSoaking the hydrogel dumbbell-shaped sample bar in a phenylenediamine/aniline/phytic acid solution at 4 ℃ for 12h, taking out the sample bar, soaking the sample bar in an ammonium persulfate solution (taking 3.51g of ammonium persulfate and 6mL of deionized water) at 4 ℃ for 12h, taking out the sample bar, and then removing ionsSoaking in water for 12h to obtain HPAMAA-Si3MQ-PANI/PPDA hydrogels. HPAMAA-Si to be obtained3MQImmersion of the-PANI/PPDA hydrogel in 0.1M FeCl3Taking out the solution and then immersing the solution in deionized water for 36h to obtain the ion-crosslinked reinforced hydrogel HPAMAA-Si3MQ-PANi/PPDA-0.1FeCl3。
1. Testing of HPAMAA-Si by surface resistivity instrument3MQ-PANi/PPDA-0.1FeCl3The hydrogel had a surface resistance of 106Omega, which shows that the hydrogel prepared in this example has good antistatic property.
2. Mixing HPAMAA-Si3MQ-PANi/PPDA-0.1FeCl3The hydrogel was subjected to a cyclic tensile test at 50% strain according to national standard GB/T1040.2-2006, the stress-strain curve of which is shown in FIG. 6.
As can be seen from FIG. 6, the maximum stress of the hydrogel at 50% strain is 0.34MPa, and the internal dissipation energy is 0.144 MJ/m3Compared with HPAMAA-Si without soaking iron ions3MQPANi/PPDA hydrogel (maximum stress 0.1MPa at 50% strain, internal energy consumption 0.043 MJ/m)3) Its strength is increased by 240% and its toughness is increased by 235%. The iron ions are effectively combined with carboxyl anions in polyacrylic acid polymer chains in the hydrogel through ion coordination after the sample strip is immersed in the ferric ion solution, so that the strength and the toughness of the sample strip are obviously improved.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (10)

1. The antistatic self-recovery triple interpenetrating network silicone hydrogel is characterized in that the silicone hydrogel comprises a carbon chain polymer formed by addition polymerization of vinyl monomers, and the carbon chain polymer is crosslinked to form a first high molecular network through hydrophobic association; silicon-containing polymers are formed by condensation polymerization of silicon monomers, and the silicon-containing polymers form a second high molecular network through hydrogen bonding; polyaniline is formed by oxidizing and polymerizing aniline monomers, and a third polymer network is formed by the polyaniline through hydrogen bonds or hydrogen bond/covalent crosslinking; the first polymer network, the second polymer network and the third polymer network are interpenetrating.
2. The antistatic self-healing triple interpenetrating network silicone hydrogel of claim 1, wherein said vinyl monomers comprise hydrophobic vinyl monomers and hydrophilic vinyl monomers, said hydrophilic vinyl monomers carrying at least one anion; the silicon monomer is one or more of hexamethyldisiloxane, ethyl orthosilicate and methyltrimethoxysilane; the aniline monomer is aniline or an aniline derivative.
3. The antistatic self-healing triple interpenetrating network silicone hydrogel of claim 1, wherein said hydrophobic vinyl monomer is stearyl methacrylate and/or cetyl methacrylate; the hydrophilic vinyl monomer is one or more of acrylamide, methacrylamide, acrylic acid and methacrylic acid.
4. A method of preparing the antistatic self-healing triple interpenetrating network silicone hydrogel of claim 1 ~ 3 comprising the steps of:
dissolving an alkene monomer, an emulsifier and an initiator in deionized water, adding a silicon-containing monomer, a catalyst and a cosolvent, uniformly stirring to obtain a mixed solution, adding the mixed solution into a glass mold, carrying out polymerization reaction at the temperature of 60 ℃ and ~ 80 ℃ for 20h and ~ 28h, and after the polymerization reaction is finished, putting the obtained hydrogel in deionized water for dialysis to obtain double-network silicon hydrogel;
immersing the double-network silicon hydrogel obtained in the step 1) into a mixed aqueous solution containing aniline monomers and a cross-linking agent, taking out the double-network silicon hydrogel, immersing the double-network silicon hydrogel into an oxidant aqueous solution for oxidative polymerization, and immersing the double-network silicon hydrogel into deionized water for 24 ~ 36 hours after the polymerization reaction is finished, thereby obtaining the triple interpenetrating network silicon hydrogel.
5. The method for preparing the antistatic self-healing triple interpenetrating network silicone hydrogel according to claim 4, wherein step 2) further comprises immersing in an aqueous solution of iron ions after oxidative polymerization, wherein the concentration of the iron ions is 0.05 ~ 0.2.2 mol/L, and the immersion time is 24 ~ 36 h.
6. The preparation method of the antistatic self-recovery triple interpenetrating network silicone hydrogel according to claim 4, wherein in the step 1), the emulsifier is cetyl trimethyl ammonium bromide or stearyl trimethyl ammonium chloride, the initiator is potassium persulfate or ammonium persulfate, the mass ratio of the emulsifier to the vinyl monomer is 0.4 ~ 0.48.48: 1, and the mass ratio of the initiator to the vinyl monomer is 0.001 ~ 0.006.006: 1.
7. The preparation method of the antistatic self-recovery triple interpenetrating network silicone hydrogel according to claim 4, wherein the total monomer concentration in the mixed solution in the step 1) is 2.5 ~ 3.0.0 mol/L, and the mass ratio of the vinyl monomer to the silicon-containing monomer is 1.0 ~ 1.3.3: 1.
8. The preparation method of the antistatic self-healing triple interpenetrating network silicone hydrogel according to claim 4, wherein the catalyst in step 1) is concentrated hydrochloric acid, the mass ratio of the catalyst to the silicon-containing monomer is 0.6 ~ 1.0.0: 1, the cosolvent is ethanol, and the mass ratio of the cosolvent to the silicon-containing monomer is 0.3 ~ 0.6.6: 1.
9. The preparation method of the antistatic self-healing triple interpenetrating network silicone hydrogel according to claim 4, wherein the concentration of aniline monomer in the mixed aqueous solution of step 2) is 0.14 ~ 0.18.18 g/mL, the cross-linking agent is phytic acid and/or p-phenylenediamine, the mass ratio of the cross-linking agent to aniline monomer is 2.3 ~ 2.7.7: 1, the mass ratio of aniline monomer to vinyl monomer is 0.15 ~ 0.25: 1, the oxidant is ammonium persulfate or potassium persulfate, and the concentration of the oxidant aqueous solution is 2.2 ~ 2.8.8 mol/L.
10. The preparation method of the antistatic self-recovery triple interpenetrating network silicone hydrogel of claim 4, wherein the temperature of the mixed aqueous solution in the step 2) is 2 ~ 8 ℃, the immersion time of the double network silicone hydrogel is 10 ~ 14h, the temperature of the oxidant aqueous solution is 2 ~ 8 ℃, and the immersion time of the double network silicone hydrogel is 10 ~ 14 h.
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