CN111171218A - Multi-phase gel with multistable mechanical and shape memory properties and preparation method thereof - Google Patents

Multi-phase gel with multistable mechanical and shape memory properties and preparation method thereof Download PDF

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CN111171218A
CN111171218A CN202010051895.7A CN202010051895A CN111171218A CN 111171218 A CN111171218 A CN 111171218A CN 202010051895 A CN202010051895 A CN 202010051895A CN 111171218 A CN111171218 A CN 111171218A
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CN111171218B (en
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刘明杰
禚淑云
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Abstract

The invention relates to a multi-phase gel with multistable mechanics and shape memory properties and a preparation method thereof. The multiphase gel has a heterogeneous network structure, a water or ionic liquid gel network is used as a matrix, and oil gel particles with the particle size of 1-20 mu m are uniformly dispersed in the matrix; the oil gel particles comprise an oil gel network and an oil phase mixed solvent filled in the oil gel network; the oil phase mixed solvent is selected from CxH2x+2Is n-alkane or the formula CxH2x+ 2A mixture of more than two of O n-alkanol, wherein x is more than or equal to 8 and less than or equal to 50; in the oil phase mixed solvent, the carbon number x of every two adjacent n-alkanes or n-alkanols in ascending order or descending order of the carbon number on the molecular chain is different by more than 6, and the oil phase solvents are mutually non-eutectic. The multi-phase gel has mechanical multi-level regulation and control performance, shape memory performance, good elasticity, stability and conductivity; has application prospect in the aspects of mechanical engineering, soft robots, medical instruments and the like.

Description

Multi-phase gel with multistable mechanical and shape memory properties and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a multi-phase gel with multistable mechanics and shape memory properties and a preparation method thereof.
Background
With the development of materials science, some materials having excellent mechanical properties have played an indispensable role in various fields. However, these materials generally have single mechanical properties and cannot adapt to changing environments, thus limiting their applications. The mechanical adjustable material has two or more stable mechanical states, and mechanical properties change under external stimulation such as heat, light, solvent and the like, so that the mechanical adjustable material shows good environmental adaptability. The current mechanics adjustable material is mainly based on shape memory material, phase change material, electromagnetic fluid and reversible cross-linked network. However, most of the materials have two mechanical states of hardness and softness, and cannot be well adapted to the complicated and changeable precision application field. Therefore, the development of the material with multiple mechanical states has very important significance and application prospect.
Gels are a class of three-dimensional network-structured polymers that swell with solvents, with hydrogels being the most common. The hydrogel is often applied to the aspects of tissue culture, medical accessories and the like due to the soft and wet characteristics of the hydrogel. The ionic liquid gel is a gel formed by taking ionic liquid as a dispersion medium, is used as a novel material, not only maintains the original property of the ionic liquid, but also solves the problem of ionic liquid overflow, and the higher plasticity of the ionic liquid gel in shape meets the requirements of people on special materials, thereby expanding the application range of the ionic liquid. Ionic liquids have many superior properties not compared to conventional liquids: high chemical and thermal stability; the vapor pressure is close to zero and is almost non-volatile; is not flammable; the ionic conductivity is high; the heat capacity is relatively large, and the like, and has important application value in various fields. The ionic liquid has the advantage of good ionic conductivity which is incomparable with other solvents, so that the largest application field of the ionic liquid gel is the construction of electrochemical materials. The almost non-volatile property of the ionic liquid improves the application safety of the ionic liquid gel in an electrochemical device, and the ionic liquid has high thermal stability, so the electrochemical device constructed by the ionic liquid gel can be generally used in a higher temperature range. As a solid electrolyte-like material, ionic liquid gel is widely used in various energy storage devices, such as super capacitors, lithium batteries, fuel cells, solar cells, and field effect transistor electronic devices. Based on the excellent properties of the ionic liquid, the ionic liquid gel has wide application in electrochemical devices, optical devices, brake sensing devices, catalysis, separation, drug delivery and other aspects.
The shape memory polymer is a polymer which can restore its original shape after being deformed and temporarily fixed into another shape after being processed by physical stimulation such as heat, light, electricity, magnetism, or by chemical stimulation such as solution. Shape memory polymers are a new class of shape memory materials that have been developed after shape memory alloys and shape memory ceramics. Shape memory polymers, as a class of organic polymer materials, exhibit many advantages over shape memory alloys and ceramics: 1) in addition to their heat-responsive properties, they are capable of responding to a variety of stimuli such as light, electric fields, magnetic fields, and solvents; 2) shape memory polymers can achieve multiple shape memory effects with a single or multiple stimuli; 3) they may have a variety of structural designs; 4) the shape memory performance can be adjusted by utilizing the methods of preparing the composite material, mixing and synthesizing; 5) has good biocompatibility and biodegradability; 6) the novel aircraft has the traditional performances of light weight, easiness in processing, low energy consumption and the like, and has great application value in the aspects of aircrafts, gas power systems, aircraft parts and the like. The shape memory gel has the advantages of high moisture retention, elasticity, biocompatibility and the like, and shows good application prospects in the fields of biomedicine, medical equipment, wound dressing and the like.
An article published by the research team of the present inventors, "high fly string, Shape memory organic hydrogels Using Phase-Transition microorganisms", z.zhao et al, adv.mater, 2017,29,1701695, discloses a Highly elastic Shape memory hydrogel material that produces a composite hydrogel in which paraffin is used in the dispersed Phase of an organogel to control the Shape memory properties of the gel. Paraffin is a common phase change material, and is a mixture of hydrocarbons with different carbon numbers, wherein the carbon chain structures are different, various components are mutually influenced to form eutectic crystals, and the phase change material has a wide phase change temperature (the temperature span is about 50-75 ℃). The wider temperature range causes the mechanical transformation and shape memory performance of the material to be limited, the controllability is poorer, the sensitivity is low, and the transformation efficiency is lower; the time of the material in the changing process is long, which is not favorable for the mechanical stability; in the aspect of shape memory, the quick recovery of the original shape is not facilitated. Moreover, the hydrogel is used as the continuous phase of the material, and due to the influence of the physical properties of water, the gel material has narrow working temperature and poor stability, and has great limitation on the selection of other components of the composite material. Therefore, it is difficult to use the material in the important fields of precision instruments, soft robots, and the like.
In summary, although the gel has been greatly researched and developed, the mechanical functionality of the gel is mostly single, so that the development of multifunctional ionic liquid gel materials with easily adjustable mechanical properties is of great significance for expanding the application field of the gel.
Disclosure of Invention
The invention aims to provide a multi-phase gel with multistable mechanical and shape memory properties and a preparation method thereof. The preparation process is simple, the obtained gel material has the characteristics of shape memory and adjustable mechanical property, can meet the requirements of modern precise instruments and functional devices, can overcome a plurality of defects in the prior art, and has important application prospects.
The invention discloses a gel material with a heterogeneous network structure prepared based on an emulsion polymerization method, wherein a high-molecular elastic network is constructed by taking water or ionic liquid as a solvent in a continuous phase, and an oil-phase mixed solvent is constructed by taking an oil-phase mixed solvent in a dispersed phase. The diameter of the dispersed phase particles is 1-20 μm.
The specific technical scheme of the invention is as follows:
the invention provides a multiphase gel with multistable mechanics and shape memory properties, which is characterized in that: the multiphase gel has a heterogeneous network structure, takes a water or ionic liquid gel network as a matrix, and the inside of the matrix is uniformly dispersed with the particle size of 1-20 μm oleogel microparticles; the oil gel particles comprise an oil gel network and an oil phase mixed solvent filled in the oil gel network; the oil phase mixed solvent is selected from CxH2x+2Is n-alkane or the formula CxH2x+2A mixture of more than two of O n-alkanol, wherein x is more than or equal to 8 and less than or equal to 50; in the oil phase mixed solvent, the carbon number x of every two adjacent n-alkanes or n-alkanols in ascending order or descending order of the carbon number on the molecular chain is different by more than 6, and the oil phase solvents are mutually non-eutectic.
The water or ionic liquid gel is a macromolecular network swelled by water or ionic liquid. The n-alkanes or n-alkanol mixtures used in accordance with the above formula have a temperature-responsive phase transition behavior with a melting temperature and a crystallization temperature.
The preparation method of the multiphase gel is characterized by comprising the following steps:
1) and fully and uniformly mixing water or ionic liquid, an organic monomer, an organic or inorganic cross-linking agent and a photoinitiator to obtain a water or ionic liquid phase mixed solution A.
2) Fully and uniformly mixing the oil phase mixed solvent, the oil phase monomer, the organic cross-linking agent and the photoinitiator to obtain an oil phase mixed solution B;
3) fully mixing the mixed solution A obtained in the step 1) with the mixed solution B obtained in the step 2) to form a stable oil-in-water emulsion or an oil-in-ionic liquid emulsion, wherein the particle size of emulsion droplets is 1-20 microns;
4) and (3) placing the emulsion prepared in the step 3) under an ultraviolet lamp for illumination to obtain the multiphase gel.
Wherein the steps 2) to 4) are carried out under the temperature condition of keeping the oil phase mixed solvent in a liquid state.
Since the n-alkane or n-alkanol component is used in the system of the present invention, if the temperature is too low, some of the oil phase solvent may become solid, which is not favorable for sufficient mixing and formation and stabilization of the emulsion structure, and thus, the steps 2) to 4) need to be performed under temperature conditions that maintain the oil phase mixed solvent in a liquid state. The temperature range is not particularly limited and may be selected depending on the particular reagents used, so that the components are maintained in liquid form, preferably at 50-90 ℃.
In order to achieve the effect of the present invention, the mixed solution is preferably processed to form an emulsion in step 3) using a high speed shearing machine or a high pressure homogenizer. The treatment time is not particularly limited as long as the emulsion can be stably formed, and generally, a treatment time of 15 seconds or more is required, and 1 to 5min is preferable in view of the effect and efficiency. In addition, the emulsion may be formed in other ways known in the art, so long as a relatively stable emulsion of the desired particle size is formed.
To enhance the emulsifying effect, an emulsifier may be added in step 1) or step 3). The emulsifier is one or more of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), tween, nonionic paraffin microemulsion, anionic paraffin microemulsion, cationic paraffin microemulsion, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and polyethylene glycol.
The emulsifier used in the invention can be completely dissolved in water, but many of the emulsifiers can not be dissolved in the ionic liquid, and in order to better achieve the effect of the invention, when the ionic liquid is used in the step 1), the emulsifier needs to be added into a small amount of water, ethanol and/or propylene glycol to be prepared into an emulsifier solution with the concentration of 1-10 wt% for use. In the process of the present invention, the amount of emulsifier used is not more than 0.1% by weight based on the mass of the whole system.
If the inorganic nanoparticle type cross-linking agent is added into the system, an emulsifier is not needed to be added, because the nanoparticles can stabilize the emulsion interface due to the hydrophilic and hydrophobic properties of the nanoparticles, and play a role in emulsification. The inorganic nanoparticle type cross-linking agent can be selected from metal oxide (such as silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, etc.) or hydroxide cluster and surface graft thereof, graphene, clay, etc.
The ultraviolet irradiation time in the step 4) is not particularly limited as long as the polymerization reaction is completed, and the irradiation is preferably performed for 1 to 3 hours.
In order to better implement the invention and achieve better mechanical properties, the volume ratio of the mixed solution A to the mixed solution B in the step 3) is preferably 1:3-10:1, and more preferably 1:1-10: 1.
The ionic liquid in step 1) can adopt various room-temperature ionic liquids in the field, and the type of the ionic liquid is not particularly limited. Imidazole room-temperature ionic liquid commonly used in the field is preferably used, the raw materials are widely applied, and the unified chemical structure of the raw materials is shown as the formula (I):
Figure BDA0002371474190000041
wherein n is more than or equal to 0 and m is less than or equal to 10.
The organic monomer in the step 1) is selected from one or more of acrylamide or acrylic acid polymerization monomers, and has the structural characteristics as shown in a formula (II):
Figure BDA0002371474190000042
among them, R1, R2 and R3 are preferably independent hydrogen or an alkyl group having 1 to 3 carbon atoms.
The oil phase monomer in the step 2) is acrylate monomer and has the structural characteristics as shown in the formula (III):
Figure BDA0002371474190000043
among them, R1 and R2 are preferably independent hydrogen or an alkyl group having 5 to 20 carbon atoms.
The organic cross-linking agent in the steps 1) and 2) is one or more of cross-linking agents of acrylate or acrylamide type, and has the structural characteristics as shown in a formula (IV):
Figure BDA0002371474190000044
among them, 1. ltoreq. n, m. ltoreq.5, R1, R2 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms are preferable.
The inorganic cross-linking agent in the step 1) is a nanoparticle type cross-linking agent, and is selected from one or more of metal oxides (such as titanium dioxide, zirconium oxide, aluminum oxide and the like), hydroxide clusters and surface grafts thereof, silicon dioxide, graphene and clay.
The photoinitiator in the steps 1) and 2) is 2, 2-dialkoxy acetophenone which has the structural characteristics as shown in the formula (V):
Figure BDA0002371474190000051
among them, R1 and R2 are preferably alkyl groups having 1 to 8 carbon atoms.
The water and/or ionic liquid phase mixed solution A in the step 1) is a clear mixed solution and has good transparency.
The oil phase mixed solution B in the step 2) has melting-crystallization phase transition behavior, the mixed solution is white solid when the temperature is lower than the lowest crystallization temperature of all the components, the mixed solution is transparent liquid when the temperature is higher than the highest melting temperature of all the components, and the mixed solution is a liquid-solid mixed solution when the temperature is between the two temperatures.
The emulsion in the step 4) is a stable oil-in-water or ionic liquid emulsion, wherein the particle size of emulsion droplets is 1-20 mu m, the emulsion has phase change behavior, and the emulsion is white or semitransparent viscous liquid.
The multiphase gel in the step 5) has a heterogeneous network structure, the water or ionic liquid gel network is a continuous phase, and the phase-change oil gel particles are a disperse phase.
In steps 1) and 2), a person skilled in the art can prepare the aqueous or ionic liquid phase mixed solution a and the oil phase mixed solution B in a manner well known in the art.
Preferably, in step 1), the mass ratio of water or ionic liquid to organic monomer is 10:1 to 1: 1; the dosage of the cross-linking agent and the photoinitiator respectively accounts for 1/1000-1/10 and 1/10000-5/1000 of the mass of the organic monomer, and the dosage of the emulsifier does not exceed 0.1 wt% of the mass of the whole system.
In the step 2), the mass fraction of each oil phase solvent is preferably (100/n +/-20)%, n is the type of the oil phase solvent, and the mass ratio of the oil phase mixed solvent to the oil phase monomer is 1:5-10: 1; the dosage of the cross-linking agent and the photoinitiator respectively accounts for 1/1000-1/10 and 1/10000-5/1000 of the mass of the oil phase monomer.
Advantageous effects
The invention discloses a gel material with a heterogeneous network structure prepared based on an emulsion polymerization method, wherein a high-molecular elastic network is constructed by taking water and/or an ionic liquid as a solvent in a continuous phase, and a high-molecular network of an oil phase is constructed by taking a mixed solution of a plurality of n-alkanes or n-alkanol with specific combinations as a solvent in a dispersed phase. The diameter of the dispersed phase particles is 1-20 μm. Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the heterogeneous structure network of the water (or ionic liquid) gel matrix and the oil gel particles uniformly dispersed in the matrix is constructed, and the components in the dispersed phase are improved, so that the mechanical property and the stability of the composite gel material are improved, and the controllable shape memory and the sensitivity of the material are greatly enhanced. The dispersed phase oleogel is characterized in that a mixture of n-alkane or n-alkanol with a certain carbon number difference is selected as a solvent, so that the temperature-induced multistage controllable shape memory function of the material is realized. Meanwhile, due to the fact that a specific internal oil phase mixed solvent is selected, the composite gel can have multistage mechanical properties, the modulus of the composite gel changes in a stepped mode along with the change of temperature, and the temperature stability and the mechanical properties are determined accordingly, so that the material has adjustable and stable mechanical properties.
(2) When the gel matrix adopts the ionic liquid, the ionic liquid has non-volatility, high temperature resistance and high conductivity, and compared with a product of the hydrogel matrix, the mechanical property of the material is improved, and the strength, the toughness and the elasticity are greatly optimized; the stability is greatly improved, the working temperature is greatly widened, and the room temperature performance is more excellent; the conductivity is improved. And the introduction of the ionic liquid can also expand the selection range of the solvent in the dispersed phase oil gel, the advantages of the ionic liquid and the combination of the specific oil phase solvent, the ionic liquid and the specific oil phase solvent complement each other, and the prepared multiphase gel shows excellent mechanical multilevel regulation and control performance, shape memory performance, stability and conductivity, and has great application prospect in the aspects of mechanical engineering, soft robots, medical instruments and the like.
(3) When the gel matrix adopts the ionic liquid, the prepared material has environmental response property, and the transparency of the material can be changed according to the environmental temperature. When the temperature is lower than the phase transition temperature, the material is completely opaque white, and when the temperature is gradually increased to be higher than the phase transition temperature, the material is gradually changed from opaque to transparent along with the successive phase transition of each component in the oil-phase mixed solvent to liquid. However, in the case of hydrogels as the matrix, the material is always opaque during the temperature change.
(4) The performance of the multiphase gel prepared by the method greatly depends on the stability and uniformity of the structure. Aiming at the problem that the ionic liquid is easy to break emulsion in the emulsification process, the emulsifier is added in the process of preparing the emulsion. The emulsifier is arranged on the interface of the ionic liquid/oil, and has the functions of stabilizing the emulsion structure, not breaking the emulsion and preventing the aggregation and fusion of oil droplets.
(5) The multiphase gel has great application prospect in the fields of mechanical engineering, soft robots, medical instruments, precise instruments and the like.
Drawings
FIG. 1: confocal laser imaging of multiphase gels;
FIG. 2: DSC (a) and rheogram (b) of a gel with a transition in the triple mechanical properties;
FIG. 3: stress-strain curves in tension (a) and compression (b) of a gel having a triple mechanical property transition;
FIG. 4: DSC (a) and rheogram (b) of a gel with a quadruple mechanical property transition;
FIG. 5: shape memory properties of the multiphase gel;
FIG. 6: optical properties of multiphase ionic liquid gels.
Detailed Description
Example 1
The room temperature stable multiphase ionic liquid gel with mechanical controllable and shape memory properties and the preparation method thereof are as follows:
1) mixing 0.3g of 1-butyl-3-methylimidazolium hexafluorophosphate, 0.2g of N, N-dimethylacrylamide (the mass ratio of 1-butyl-3-methylimidazolium hexafluorophosphate to N, N-dimethylacrylamide is 1.5:1), 3mg of ethylene glycol dimethacrylate (accounting for 1/100 of the mass of 1-butyl-3-methylimidazolium hexafluorophosphate) and 0.3mg of 2, 2-diethoxyacetophenone (accounting for 1/10000 of the mass of 1-butyl-3-methylimidazolium hexafluorophosphate), adding 2mg of a sodium dodecyl sulfate aqueous solution with the mass fraction of 5%, and fully mixing uniformly to obtain an ionic liquid phase mixed solution;
2) mixing 0.29g of hexadecane, 0.29g of hexadecane (accounting for 50 percent of the hexadecane and the hexadecane respectively), 0.29g of octadecyl methacrylate, 2.9mg of ethylene glycol dimethacrylate (accounting for 1/100 of the weight of the octadecyl methacrylate) and 1mg of 2, 2-diethoxyacetophenone (accounting for 3/1000 of the weight of the octadecyl methacrylate), heating in a water bath at the temperature of about 80 ℃, and uniformly mixing to obtain an oil phase mixed solution;
3) adding the solution prepared in the step 1) into the solution obtained in the step 2), and heating in a water bath at the temperature of about 80 ℃; placing the obtained solution in a high-speed shearing machine, and shearing for 5min to obtain a white emulsion;
4) placing the emulsion prepared in the step 3) under an ultraviolet lamp for illumination for 1h to obtain the multiphase ionic liquid gel, wherein the structure of the multiphase ionic liquid gel is shown in figure 1. The multiphase gels of examples 2-4 of the present invention also have a structure similar to that of figure 1. From fig. 1, the heterogeneous network structure of the gel can be seen, in which the dispersed phase is oil gel microspheres and the continuous phase is ionic liquid gel (or hydrogel).
Example 2
The room temperature stable multiphase ionic liquid gel with mechanical controllable and shape memory properties and the preparation method thereof are as follows:
1) 0.25g of 1-hexyl-3-methylimidazolium hexafluorophosphate, 0.25g of N, N-dimethylacrylamide (mass ratio of 1-butyl-3-methylimidazolium tetrafluoroborate to N, N-dimethylacrylamide is 1:1), 2.5mg of ethylene glycol dimethacrylate (accounting for 1/100 of the mass of 1-butyl-3-methylimidazole tetrafluoroborate) and 1mg of 2, 2-diethoxyacetophenone (accounting for 4/1000 of the mass of 1-butyl-3-methylimidazole tetrafluoroborate) are mixed, and after the mixture is fully mixed, 2mg of a 1% poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (the average molecular mass is 12600) aqueous solution is added to obtain an ionic liquid phase mixed solution;
2) mixing 0.43g of trioxadecane, 0.43g of stearyl methacrylate, 4.3mg of ethylene glycol dimethacrylate (accounting for 1/100 of the mass of the stearyl methacrylate) and 0.4mg of 2, 2-diethoxyacetophenone (accounting for 1/1000 of the mass of the stearyl methacrylate), heating in a water bath at the temperature of about 80 ℃, and uniformly mixing to obtain an oil-phase mixed solution;
3) adding the solution prepared in the step 1) into the solution obtained in the step 2), and heating in a water bath at the temperature of about 80 ℃; placing the obtained solution in a high-speed shearing machine, and shearing for 3min to obtain a white emulsion;
4) placing the emulsion prepared in the step 3) under an ultraviolet lamp for illumination for 1.5h to obtain the multiphase ionic liquid gel. The thermodynamic and mechanical curves are shown in fig. 2. From fig. 2, it can be seen that the gel has three-stage phase transition characteristics over a wide temperature range, showing a modulus that varies stepwise with temperature.
Example 3
The multiphase hydrogel with mechanical adjustable and shape memory properties and the preparation method thereof are as follows:
1) mixing 0.4g of water, 0.1g of N, N-dimethylacrylamide (the mass ratio of water to N, N-dimethylacrylamide is 4:1), 32mg of XLS type clay chips (accounting for 8/100 of the mass of water) and 1mg of 2, 2-diethoxyacetophenone (accounting for 2.5/1000 of the mass of water), and fully and uniformly mixing to obtain a water-phase mixed solution;
2) mixing 0.22g of hexadecane, 0.22g of octacosane, 0.22g of hexadecanol (33% of hexadecane, octacosane and hexadecanol respectively), 0.21g of lauryl methacrylate, 1mg of ethylene glycol dimethacrylate (5/1000 of lauryl methacrylate) and 1mg of 2, 2-diethoxyacetophenone (5/1000 of lauryl methacrylate) in a water bath, heating the mixture in the water bath at the temperature of about 80 ℃, and uniformly mixing to obtain an oil phase mixed solution;
3) adding the solution prepared in the step 1) into the solution obtained in the step 2), and heating in a water bath at the temperature of about 80 ℃; placing the obtained solution in a high-speed shearing machine, and shearing for 3min to obtain a white emulsion;
4) and (3) placing the emulsion prepared in the step 3) under an ultraviolet lamp for illumination for 2h to obtain the multiphase hydrogel. The mechanical properties are shown in fig. 4. As can be seen from FIG. 4, the gel has a four-stage phase transition characteristic over a wide temperature range, exhibiting a modulus that varies stepwise with temperature. Therefore, compared with the hydrogel in the prior art, the composite hydrogel prepared by selecting the specific oil phase mixed solvent has more mechanical stable states, and the controllable shape memory and the sensitivity of the material are greatly enhanced. The mechanical properties are summarized in table 1.
TABLE 1 mechanical Properties of triple transition oil-hydrogels at different temperatures
Figure BDA0002371474190000081
Error bars are standard deviation (n ═ 6).
Example 4
The room temperature stable multiphase ionic liquid gel with mechanical controllable and shape memory properties and the preparation method thereof are as follows:
1) mixing 0.45g of 1-butyl-3-methylimidazole methyl sulfonate, 0.05g of acrylic acid (the mass ratio of the 1-butyl-3-methylimidazole methyl sulfonate to the acrylic acid is 9:1), 2.25mg of ethylene glycol diethyl acrylate (accounting for 5/1000 of the mass of the 1-butyl-3-methylimidazole methyl sulfonate) and 1mg of 2, 2-diethoxyacetophenone (accounting for 2.2/1000 of the mass of the 1-butyl-3-methylimidazole methyl sulfonate), and fully and uniformly mixing to obtain an ionic liquid phase mixed solution;
2) mixing 0.17g of hexadecane, 0.19g of octacosane, 0.18g of hexadecane, 0.17g of tetratetradecane (19.1%, 21.3%, 20.2% and 19.1% of hexadecane, octacosane, hexadecane and tetratetradecane respectively), 0.18g of octadecyl methacrylate, 0.9mg of ethylene glycol dimethacrylate (5/1000 of the octadecyl methacrylate) and 0.1mg of 2, 2-diethoxyacetophenone (5/1000 of the octadecyl methacrylate) in a water bath, heating at about 80 ℃, and uniformly mixing to obtain an oil-phase mixed solution;
3) adding the solution prepared in the step 1) into the solution obtained in the step 2), adding 2mg of a poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (with the average molecular mass of 12600) glycol solution with the mass fraction of 3%, and heating in a water bath at the temperature of about 80 ℃; placing the obtained solution in a high-speed shearing machine, and shearing for 3min to obtain a white emulsion;
4) placing the emulsion prepared in the step 3) under an ultraviolet lamp for illumination for 1h to obtain the multiphase ionic liquid gel. The shape memory properties and optical properties are shown in fig. 5 and 6. As can be seen in fig. 5, the gel sheet can fold and deform it into a temporary shape above the phase transition temperature and fix the temporary shape below the phase transition temperature, and when the temperature is raised again to the phase transition temperature, the gel sheet returns to a permanent shape. As can be seen from FIG. 6, the optical properties of the ionic liquid gel of the present invention can vary with the environment, and is opaque at room temperature and has high transparency at 45 ℃. The mechanical properties of the gel are shown in table 2, the material has five mechanical transformations, 6 stable modulus platforms.
TABLE 2 mechanical Properties of quintuple transition oil-ionic liquid gel at different temperatures
Figure BDA0002371474190000091
Error bars are standard deviation (n ═ 6).

Claims (16)

1. A multi-phase gel having multistable mechanical and shape memory properties, characterized by: the multiphase gel has a heterogeneous network structure, a water or ionic liquid gel network is used as a matrix, and oil gel particles with the particle size of 1-20 mu m are uniformly dispersed in the matrix; the oil gel particles comprise an oil gel network and an oil phase mixed solvent filled in the oil gel network; the oil phase mixed solvent is selected from CxH2x+2Is n-alkane or the formula CxH2x+2A mixture of more than two of O n-alkanol, wherein x is more than or equal to 8 and less than or equal to 50; in the oil phase mixed solvent, the carbon number x of every two adjacent n-alkanes or n-alkanols in ascending order or descending order of the carbon number on the molecular chain is different by more than 6, and the oil phase solvents are mutually non-eutectic.
2. A method of preparing a multiphase gel in accordance with claim 1, comprising the steps of:
1) fully and uniformly mixing water or ionic liquid, an organic monomer, an organic or inorganic cross-linking agent and a photoinitiator to obtain a water or ionic liquid phase mixed solution A;
2) fully and uniformly mixing the oil phase mixed solvent, the oil phase monomer, the organic cross-linking agent and the photoinitiator to obtain an oil phase mixed solution B;
3) fully mixing the mixed solution A obtained in the step 1) with the mixed solution B obtained in the step 2) to form a stable oil-in-water emulsion or an oil-in-ionic liquid emulsion, wherein the particle size of emulsion droplets is 1-20 microns;
4) placing the emulsion prepared in the step 3) under an ultraviolet lamp for illumination to obtain multiphase gel;
wherein the steps 2) to 4) are carried out under the temperature condition of keeping the oil phase mixed solvent in a liquid state.
3. The method of claim 2, wherein: and 3) treating the mixed solution by using a high-speed shearing machine or a high-pressure homogenizer to form emulsion.
4. The method of claim 2, wherein: the volume ratio of the mixed solution A to the mixed solution B in the step 3) is 1:3-10: 1.
5. The method of claim 2, wherein: adding an emulsifier in the step 1) or the step 3), wherein the emulsifier is one or more of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), tween, a nonionic paraffin microemulsion, an anionic paraffin microemulsion, a cationic paraffin microemulsion, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and polyethylene glycol.
6. The production method according to any one of claims 2 to 5, characterized in that: the ionic liquid in the step 1) is room-temperature ionic liquid.
7. The production method according to any one of claims 2 to 5, characterized in that: the organic monomer in the step 1) is selected from one or more of acrylamide or acrylic acid polymerization monomers.
8. The production method according to any one of claims 2 to 5, characterized in that: the oil phase monomer in the step 2) is acrylate monomer.
9. The production method according to any one of claims 2 to 5, characterized in that: the organic cross-linking agent in the steps 1) and 2) is one or more of acrylic ester or acrylamide type cross-linking agents.
10. The production method according to any one of claims 2 to 5, characterized in that: the inorganic cross-linking agent in the step 1) is a nanoparticle type cross-linking agent, and is selected from one or more of metal oxide, hydroxide cluster and surface graft thereof, graphene and clay.
11. The production method according to any one of claims 2 to 5, characterized in that: the photoinitiator in the steps 1) and 2) is 2, 2-dialkoxy acetophenone.
12. The production method according to any one of claims 2 to 5, characterized in that: the mass ratio of the water or the ionic liquid to the organic monomer in the step 1) is 10:1-1:1, and the dosages of the cross-linking agent and the photoinitiator respectively account for 1/1000-1/10 and 1/10000-5/1000 of the mass of the organic monomer.
13. The production method according to any one of claims 2 to 5, characterized in that: in the step 2), the mass fraction of each oil phase solvent is (100/n +/-20)%, n is the type of the oil phase solvent, the mass ratio of the oil phase mixed solvent to the oil phase monomer is 1:5-10:1, and the dosage of the cross-linking agent and the photoinitiator respectively accounts for 1/1000-1/10 and 1/10000-5/1000 of the mass of the oil phase monomer.
14. The method of claim 5, wherein: the amount of the emulsifier is not more than 0.1 wt% of the mass of the whole system.
15. The production method according to any one of claims 2 to 5, characterized in that: steps 2) to 4) are preferably carried out at a temperature of 50 to 90 ℃.
16. Use of the multiphase gel of claim 1 in the fields of mechanical engineering, soft body robotics, medical devices, precision instruments.
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