WO2021109323A1 - 可逆动态大孔弹性体聚合物材料及其制备方法和应用 - Google Patents
可逆动态大孔弹性体聚合物材料及其制备方法和应用 Download PDFInfo
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- polymer material
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- elastomeric polymer
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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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—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 esters
- C08J2333/14—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 esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Definitions
- the invention relates to the technical field of polymer materials, in particular to a reversible dynamic macroporous elastomer polymer material and a preparation method and application thereof.
- Macroporous polymers are a kind of materials with interpenetrating or closed pore structures composed of polymers as the base material, and the main cavity diameter is above 50 nanometers (according to the international IUPAC standard). Macroporous polymers can combine the advantages of both macroporous materials and polymers. In addition to the large surface area and adjustable pore size of the macroporous material itself, it also has high mechanical strength, good thermal stability, and good solvent resistance. , Easy processing, low raw material prices, etc., has been widely used in catalysis, energy storage, sound insulation, gas separation, water treatment, drug delivery and other fields.
- the diversity of polymer synthesis methods can provide a wealth of synthesis paths to construct pore structures with different properties, and can provide a wider range of applications for macroporous materials, such as anti-fouling and drag reduction interfaces, reflective coatings, fluorescence detection, Energy transfer, liquid storage, tissue engineering scaffolds, cell culture and other new application scenarios, so it is considered to be one of the most promising porous materials.
- macroporous materials such as anti-fouling and drag reduction interfaces, reflective coatings, fluorescence detection, Energy transfer, liquid storage, tissue engineering scaffolds, cell culture and other new application scenarios, so it is considered to be one of the most promising porous materials.
- phase separation polymerization free-drying, gas-blowing, and templating methods, etc. .
- the phase separation polymerization method is the earliest method used to prepare porous polymers. Its mechanism is that the diluent that is compatible with the precursor phase separates during the polymerization or cross-linking process, and the diluent aggregates domains are formed in situ as a cavity template. , These areas can be removed after polymerization to obtain a permanent porous structure. Various polymerizable monomers and crosslinkable polymer precursors can be prepared by this method to obtain macroporous polymers.
- the diluent can be a solvent, a non-solvent (such as supercritical carbon dioxide), or an inert polymer.
- the suspension polymerization method commonly used to prepare porous polymer beads belongs to this method. This method requires the polymerization/crosslinking kinetics to match the phase separation kinetics, and the obtained pore size distribution is relatively broad, which often involves a relatively complicated diluent removal process.
- the freeze-drying method is a method that has emerged in recent years. It mainly uses the water crystals in the freeze-drying process to drive the irreversible aggregation of the polymer in the system, thereby obtaining a porous polymer after removing the solvent. This method consumes a lot of energy, and the mechanical properties of the macroporous polymer obtained are relatively poor.
- the foaming method is a method that uses foaming agents to generate bubbles as a template during the curing of the material, and is widely used in industries such as artificial leather and sponges.
- the template method is a method of preparing a porous polymer using a porogen that is insoluble in a polymer precursor (a mixed precursor of a monomer and a crosslinking agent or a crosslinkable polymer precursor) as a cavity template. Generally, it includes three steps: firstly disperse the porogen into the precursor; then initiate polymerization or crosslinking to form a continuous polymer phase; finally, leaching and eluting the porogen to obtain a macroporous material. This method is suitable for various monomers and polymers.
- the cavity structure and pore size can be precisely controlled by the template (which can be small molecules, micro-nano particles or continuous frameworks), which is convenient for preparing large-area samples; but the process is relatively complicated, especially The leaching process is time-consuming, high-cost, and easy to cause material deformation.
- the template which can be small molecules, micro-nano particles or continuous frameworks
- the current preparation methods of macroporous polymers often involve volatile organic solvents or consume large amounts of energy or time, and the prepared macroporous structures are often permanent, and generally cannot change their topology under external stimuli. structure.
- the properties of macroporous polymers are usually determined by the material composition and pore structure.
- the current strategy for preparing smart macroporous polymers is mainly to select stimulus-responsive polymers as the base material or modify the pore surface through responsive molecules to achieve the purpose of changing the material properties; and to adjust the macroporous polymer materials by changing the pore topology
- Controlling the opening and closing of pores is one of the most effective ways to adjust the performance of porous materials.
- the current method is to modify the responsive molecules in the pores, through external stimuli, such as light, pH, salt, recognition molecules, electrical signals, etc., to change the topological structure and properties of these molecules to prevent the entry and output of specific substances.
- So as to achieve the internal performance of the switch material such as catalytic properties, transport capacity, optical performance and other aspects.
- these changes at the molecular level can only be used in systems with relatively small pore sizes (a few nanometers), and it is difficult to open up the macroporous structure.
- the purpose of the present invention is to provide a reversible dynamic macroporous elastomeric polymer material and its preparation method and application.
- the technical solutions of the present invention to solve the above technical problems are as follows:
- a method for preparing a reversible dynamic macroporous elastomeric polymer material includes the following steps:
- the template liquid is a volatile solution that is incompatible with the mixed precursor, or is a volatile solution that is incompatible with the crosslinkable polymer precursor;
- the curing precursor is applied to the substrate or mold for curing to prepare a reversible dynamic macroporous elastomeric polymer material.
- the polymerizable monomer of the present invention refers to a small molecule monomer that can undergo polymerization under the action of a crosslinking agent.
- the cross-linkable polymer precursor of the present invention refers to a polymer capable of forming a covalent bond cross-link, and a cross-linking catalyst, a free radical initiator, an oil-soluble organic pigment and a surfactant can be optionally added.
- polymerizable monomers or crosslinkable polymer precursors are used as raw materials to mix with the template liquid.
- the template solution is a volatile solution that is incompatible with the polymerizable monomers or crosslinkable polymer precursors.
- the template liquid and the precursor are used (Including polymerizable monomers and cross-linkable polymer precursors, the same applies below) incompatibility so as to form a template for the formation of pore structure during the polymerization and cross-linking process.
- the template solution due to the volatility of the template solution, it can During the curing process, it volatilizes, so that the space originally occupied by the template liquid forms a pore structure after volatilization, thereby obtaining a porous and macroporous elastomeric polymer.
- the pore structure collapses.
- the original pore structure supported by the template liquid becomes a collapsed solid state under the action of gravity, but the pores actually exist, and when the porous elastomer receives external stimuli At this time, the collapsed pores are restored to open, thereby realizing the reversible conversion between the solid state and the porous state.
- the cross-linking polymerization of the precursor itself and the volatilization of the template liquid can be controlled by means to adjust and control the pore structure, thereby obtaining reversible dynamic macropores with different properties.
- Elastomer polymer material
- the template liquid of the present invention can be randomly distributed in the solidified precursor in the form of countless small droplets, or embedded in the solidified precursor in a specific shape (fiber, pattern or three-dimensional array).
- the specific form is based on the template liquid and the precursor.
- the way the body is mixed is related. For example, by stirring and mixing, the template liquid is dispersed into numerous small droplets, or by injection, the template liquid is formed into a fibrous liquid in the solidified precursor.
- the method of applying the cured precursor to the substrate or mold in the present invention includes, but is not limited to, pouring, brushing, spraying, and spin coating processes.
- the curing precursor can be prepared directly on the base or mold without pre-mixing, that is, a mixed precursor of a polymerizable monomer and a crosslinking agent or a crosslinkable polymer precursor. It is applied to the substrate or in the film tool, and then the template liquid is introduced to obtain a solidified precursor.
- Those skilled in the art can select a suitable method according to the performance requirements of the required porous elastomer material.
- the localization and patterning of the porous structure can be realized by the method of sequential casting. For example, first cast a mixed precursor containing a polymerizable monomer and a crosslinking agent or a crosslinkable polymer precursor on the film tool to obtain a specific model, and then cast a mixture of the corresponding precursor and water in the blank area, and the obtained product is completely cured. A whole material has a porous structure only in specific areas after stimulation.
- a mixed precursor containing a polymerizable monomer and a cross-linking agent or a cross-linkable polymer precursor can be cast and cured in a film tool to obtain a reverse elastomer film tool, and the corresponding precursor and water can be poured into the film tool.
- the mixed precursor after mixing is cured to obtain a transparent elastomer material. Under external stimuli, the responsive part of this material will become porous, showing a specific pattern macroscopically.
- a cavity structure with a specific geometric structure can be prepared in combination with a printing method, or only one cavity can be prepared.
- a viscous mixed precursor containing polymerizable monomers and cross-linking agents or cross-linkable polymer precursors an aqueous solution is injected to print graphics, and after curing, a transparent solid polymer material is obtained, which can become porous under external stimuli To show the printed pattern.
- a channel that opens and closes under external stimuli can be obtained.
- the organic silica gel precursor is poured on the substrate, and the polyvinyl alcohol aqueous solution is injected into the viscous precursor through the needle to form a fibrous water template that runs through the precursor. After curing, a transparent silicone elastomer is obtained. This elastomer is stimulated by the outside world. A microchannel will appear at the water template.
- the size of the droplets in the obtained emulsion can be adjusted by the stirring time of the mixture of the polymerizable or crosslinkable precursor and the template solution, thereby adjusting the pore size of the obtained porous elastomeric polymer material.
- the stirring time of the mixture of the crosslinkable polymer precursor and water is 5-50 minutes, which corresponds to a droplet size of 30-1 microns.
- the present invention can prepare anisotropic materials by stretching the sample orientation sample during the curing process.
- the crosslinkable polymer precursor is mixed with an aqueous solution of polyvinyl alcohol to obtain an emulsion, and then pre-cured for 5-30 minutes under a sealed condition of 50-90°C.
- the obtained elastomer is stretched to different degrees, for example, 110-250% of the original sample, volatilized and finally solidified under open conditions, to obtain an anisotropic macroporous polymer.
- the prepared time-acting polymer exhibits different responsiveness under stimuli from different directions.
- the curing process in step (2) is performed in an open environment, and the curing temperature is room temperature or not higher than the boiling temperature of the template liquid.
- the curing process occurs naturally in an open room temperature environment, and the template liquid naturally volatilizes; it can also be heated at a temperature not higher than the boiling point of the template liquid to promote faster volatilization of the template liquid.
- curing and template liquid volatilization are carried out at the same time.
- step (2) includes the following steps:
- the intermediate is finally cured, and the curing temperature is room temperature or lower than 200°C to prepare a reversible dynamic macroporous elastomeric polymer material.
- the present invention divides the curing into three stages of pre-curing, volatilization and final curing by controlling the curing conditions. The mechanism of each stage is explained separately below.
- Pre-curing is carried out in the presence of the template liquid to form a part of the permanent cross-linked polymer structure.
- This part of the cross-linked polymer is referred to as the first network, which has the tendency to maintain the geometric shape of the sample in the state of containing the template liquid.
- the template liquid does not volatilize. And in the pre-curing process, it can be carried out at room temperature, or under a heating state not higher than the boiling point of the template liquid. If heating is used for pre-curing, the heating temperature should not be higher than the boiling point of the template liquid or the volatile substances in the template liquid.
- the template liquid contained in the pre-cured body is completely volatilized or the volatile substances in the template liquid are completely volatilized in an open state or a negative pressure state.
- negative pressure is generated inside the material; this negative pressure causes the cavity inside the material to collapse, resulting in a visually solid structure with an interface where the original template liquid is located microscopically, where this interface is referred to as Wrinkled.
- the second network for short, which has a tendency to maintain the collapsed state of the polymer material.
- the resulting material is a polymer in a collapsed state, which exhibits the characteristics of a non-porous material. For example, the material can exhibit good transparency.
- a polymer in a collapsed state is called a solid polymer for short. In fact, the state of mind is maintained by the interaction between the second network and the fold interface.
- a porous elastomeric polymer material with a first network structure, wrinkles and a second network structure is obtained.
- the cavity structure will open to obtain a macroporous polymer , This state is referred to as the porous state for short; the cavity structure in the porous state has geometric characteristics close to but slightly smaller than the original template liquid.
- the porous structure collapses, the cavity in the porous state disappears, and it returns to the solid state again. Therefore, through external stimulus conditions, the porous elastomeric polymer material can switch between a solid state and a porous state, and exist stably without specific stimuli.
- the content of the template liquid in the curing precursor is 5-90 wt%.
- the porosity of the finally obtained polymer material can be adjusted by controlling the content of the template liquid in the curing precursor.
- the porosity formed is between 4 and 80%.
- the above-mentioned polymerizable monomer is a non-volatile monomer or a monomer with a boiling point higher than 150° C. or a mixture of both.
- the above-mentioned polymerizable monomer is 4-hydroxybutyl acrylate, isooctyl acrylate, poly(ethylene glycol) methyl ether acrylate, octamethylcyclotetradecane One or more combinations of silyl ether, methylcyclopentadiene dimer and dicyclopentadiene;
- the crosslinking agent is 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate Ester, 1,2-ethylene glycol diacrylate, 1,2-ethylene glycol dimethacrylate, poly(ethylene glycol) diacrylate and poly(ethylene glycol) dimethacrylatekind or multiple combinations;
- the template liquid is water, polyvinyl alcohol aqueous solution, polyethylene oxide aqueous solution, ethanol, isopropanol, ether or n-hexane.
- the mixed precursor further includes an initiator and/or a thickener.
- the initiator and thickener can be optionally added according to the properties of the polymerizable monomer.
- the polymerizable monomer is 4-hydroxybutyl acrylate
- the initiator can be selected as azobisisobutyronitrile
- the thickener can be selected as Poly(4-hydroxybutyl acrylate).
- the crosslinkable polymer precursor is double-end acrylated polypropylene, double-end acrylated polytetrahydrofuran, double-end acrylated polypropylene, and double-end mercapto groups.
- the template liquid is water, polyvinyl alcohol aqueous solution, poly(N-isopropylacrylamide) aqueous solution, ethanol, isopropanol, ether or n-hexane.
- the organic silica gel used in the embodiment of the present invention may be a commercially available room temperature curing AB silica gel whose components are mixed 1:1, or may be a commercially available transparent liquid silica gel.
- silica gel is used as a cross-linkable polymer precursor, and a poly(N-isopropylacrylamide) aqueous solution is used as a template liquid.
- the responsive polymer After curing, the responsive polymer will be deposited on the cavity/wrinkle surface to form a chemical composition A macroporous polymer that can change both the geometry of the cavity and the geometry of the cavity.
- the crosslinkable polymer precursor also includes one or more combinations of crosslinking catalysts, free radical initiators, oil-soluble organic pigments and surfactants, crosslinking
- the catalyst is a tin catalyst or a platinum catalyst.
- the reaction activity of the silica gel precursor can be improved by adding a platinum catalyst to the silica gel. In this case, it can be cured at room temperature. As another embodiment, it is also possible to directly increase the reaction activity and promote the curing process by heating.
- oil-soluble organic pigments are mixed in a catalyst-containing silica gel precursor to prepare colored macroporous polymers.
- the present invention controls the structure of the pores by adding surfactants.
- a mixture of organic silica gel precursor and water can prepare closed-pore macroporous polymers, while in a mixture of organic silica gel precursor and water containing surfactants, when the water content is greater than 40% of the total volume, A macroporous polymer with an open-pore structure can be prepared.
- the solid state and the porous state of the reversible dynamic macroporous elastomeric polymer material of the present invention have different material density, light transmittance or surface roughness.
- the cavity portion can be used to store liquid, and exhibits significantly higher swelling properties than the bulk polymer material.
- the aforementioned stimulus responsiveness includes, but is not limited to, mechanical force responsiveness, humidity responsiveness, and solvent responsiveness.
- the above-mentioned reversible dynamic macroporous elastomeric polymer material is used in an energy-saving coating.
- the macroporous polymer can be adjusted to switch between the solid state and the porous state.
- the reversible dynamic macroporous elastomeric polymer material can transmit sunlight in the solid state to achieve the heating effect, and in the porous state, it can reflect sunlight on the one hand and heat radiation on the other hand to dissipate heat, thereby achieving a cooling effect.
- the above-mentioned materials can be made into a coating and coated on a coating that can absorb sunlight.
- the light-absorbing layer can increase the heating effect in a solid state.
- the reversible dynamic macroporous elastomer polymer material of the present invention is prepared into a coating material, which can achieve the following excellent properties: first, in fact, both the mental state and the porous state can exist stably between minus 200 degrees and 250 degrees; second, , After treatment at a temperature between minus 200 degrees and 250 degrees, it can maintain its mechanical responsiveness after returning to room temperature; third, in fact, the mental state and the porous state can exist stably in a humid environment and a rainy environment, and maintain Its mechanical responsiveness; fourth, in fact, both mental states and porous states can exist stably under solar radiation and maintain their mechanical responsiveness.
- the above-mentioned reversible dynamic macroporous elastomeric polymer material is used in a smart interface.
- the reversible dynamic macroporous elastomer polymer still maintains its stimulus responsiveness after cutting the inside; the cut interface has low surface roughness in the solid state, the water contact angle is relatively low, and the water droplet rolling angle is high. It is a non-superhydrophobic interface; after being transformed into a porous state, the cut interface has a relatively good surface roughness, high water contact angle, and water droplets are easy to roll, which is a superhydrophobic interface.
- the above-mentioned reversible dynamic macroporous elastomeric polymer material is used in liquid storage and extended surface smoothness.
- the polymer changes from a solid state to a porous state, and these cavities can be used to store the swelling liquid.
- the liquid molecules stored in the cavity can diffuse to the surface to maintain surface lubrication.
- the porous structure can increase the storage capacity of liquid molecules so as to extend the time that the surface maintains lubricating properties.
- the above-mentioned reversible dynamic macroporous elastomeric polymer material is used in fluid control.
- the macroporous elastomeric polymer material with communicating pores/channels does not allow fluid (gas or liquid) to pass through in the solid state, but allows fluid to pass through in the porous state.
- the above-mentioned reversible dynamic macroporous elastomeric polymer material is used for volume change.
- the tangential force of the macroporous elastomeric polymer material will change from a solid state to a porous state, and at the same time the volume will increase significantly. This phenomenon can be used for bottle mouth sealing and also for fixing objects.
- the macroporous elastomeric polymer material absorbs energy during the process of transforming from a porous state to a solid state, and plays a role of damping and protection.
- the porous organic elastic polymer material prepared by the invention has a controllable pore structure, overall volume and light transmittance. It has good reflection performance for sunlight and high permeability for infrared light in the atmospheric window, and can realize the conversion between the multi-empty state and the physical state under the action of external mechanical force, thereby realizing itself
- the adjustment of optical performance realizes the reflection and absorption of responsive sunlight, and then adjusts the heat absorption and heat release behavior of the material.
- the novel elastomeric polymer material with reversible dynamic porous structure of the present invention has simple and easy synthesis process, green environmental protection, high yield, low preparation cost and easy promotion.
- the reversible dynamic macroporous elastomer polymer material of the present invention has an adjustable reversible multi-layered pore structure, has good convertible sunlight reflection performance and infrared radiation performance, belongs to a macroporous polymer, and is used in radiant cooling and solar heating. have a broad vision of application.
- Figure 1 is a schematic diagram of the manufacturing principle of a reversible dynamic macroporous elastomeric polymer material according to an embodiment of the present invention
- Figure 2 is the reversible stimulus response hollowing behavior of the reversible dynamic macroporous elastomeric polymer material according to an embodiment of the present invention
- FIG. 3 is a sample diagram of the reversible dynamic porous elastomeric polymer in different preparation stages of an embodiment of the present invention
- Figure 4 is an optical microscope view of the reversible dynamic macroporous elastomeric polymer material under tension or pressure according to an embodiment of the present invention
- FIG. 5 is a diagram showing the changes of the reversible dynamic macroporous elastomeric polymer material of the embodiment of the present invention before and after force/solvent stimulation by setting the pattern "human";
- Fig. 6 is a variation diagram of the reversible dynamic macroporous elastomeric polymer material of the embodiment of the present invention that the channel can be opened and closed under external stimuli;
- Fig. 7 is a closed-pore microscope view of a reversible dynamic macroporous elastomeric polymer material prepared by a solidified precursor with a water content of 15% according to an embodiment of the present invention
- FIG. 8 is a microscopic view of an open hole prepared by a reversible dynamic macroporous elastomeric polymer material of an embodiment of the present invention through a cured precursor with a water content of 90%;
- Figure 9 is a microscope view of a macroporous elastomeric polymer with a multi-layered pore structure according to an embodiment of the present invention.
- FIG. 10 is a graph showing the relationship change between solidified precursors with different water content and porosity of the reversible dynamic macroporous elastomeric polymer material of an embodiment of the present invention.
- FIG. 11 is a graph showing changes in optical properties of an anisotropic reversible dynamic macroporous elastomeric polymer material in which the sample is stretched to 250% during the final curing process of the embodiment of the present invention under the action of mechanical forces at different angles;
- Fig. 12 is a graph showing changes in optical properties of the reversible dynamic macroporous elastomeric polymer material in a solid state and a porous state according to an embodiment of the present invention
- Figure 13 is an actual heating effect diagram of a macroporous elastomeric polymer coating of an embodiment of the present invention in a solid state;
- Figure 14 is a diagram of the actual cooling effect of the macroporous elastomeric polymer coating in the porous state of the embodiment of the present invention.
- Figure 15 is the density of the reversible dynamic macroporous elastomeric polymer material in the solid state and the porous state according to an embodiment of the present invention
- 16 is a view showing the effect of the reversible dynamic macroporous elastomeric polymer material in a solid state and a porous state in water according to an embodiment of the present invention
- Figure 17 is a contact angle diagram of water droplets on the surface of the reversible dynamic macroporous elastomeric polymer material of an embodiment of the present invention.
- Fig. 18 is a graph showing the relationship between porosity and swelling rate of the reversible dynamic macroporous elastomeric polymer material in silicone oil according to an embodiment of the present invention.
- the concentration of the platinum catalyst solution used is 1% by weight, and the product information is platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex Xylene solution of compound, Pt ⁇ 2%.
- AB silica gel and transparent organic silica gel precursors are commercially available.
- concentration of the polyvinyl alcohol aqueous solution is 1 wt%.
- Figure 1 shows the principle diagram of the preparation of the reversible dynamic macroporous polymer in the embodiment of the present invention.
- the present invention combines the polymerizable/crosslinked precursors (ie the above-mentioned polymerizable monomers and crosslinkable polymer precursors) with the incompatible And the volatile template liquid is mixed, and the monomer undergoes a solidification reaction in the presence of the template liquid.
- the template liquid also continues to play.
- the space originally occupied by the volatilized template liquid source of macropores
- the space originally occupied by the volatilized template liquid is under the action of gravity. It collapses to form a wrinkled and solid state.
- Fig. 3 is a general process of preparation in an embodiment of the present invention, showing the state of samples at different stages.
- the following examples use different monomers and corresponding template solutions to synthesize reversible macroporous elastomer polymers with different properties. Due to different materials, each example also has a corresponding stimulus method to achieve reversibility in the state. Place application.
- the present invention includes but is not limited to the following examples. The following examples are only used to illustrate the present invention and do not have a limiting effect.
- the reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- the reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- a mixture of 10 g of A and 10 g of B was used to obtain a silicone precursor.
- the silicone precursor and 3 g of an aqueous solution containing 1 wt% polyvinyl alcohol were mixed and stirred for 30 minutes, and the obtained emulsion was cast on a substrate and cured at room temperature for 6 days to prepare a reversible dynamic macroporous elastomeric polymer material.
- the reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- a 1% platinum catalyst solution was added to a mixture of 20 g and 2 g of the silica gel precursor, and mixed to obtain an organosilicon precursor with high reactivity.
- the silicone precursor and 3.4 g of an aqueous solution containing 1 wt% polyvinyl alcohol were mixed and stirred for 30 minutes, and the obtained emulsion was cast on a substrate and cured at room temperature for 6 days to prepare a reversible dynamic macroporous elastomeric polymer material.
- the reversible dynamic macroporous elastomeric polymer material containing a heterogeneous structure prepared in this embodiment is a transparent material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 5 minutes, and the obtained emulsion was cast on the substrate and pre-cured at 70°C for 20 minutes to obtain an opaque film material.
- the opaque film continued to open at 70°C.
- a transparent reversible dynamic macroporous elastomer polymer material was prepared.
- the reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3g of the aqueous solution containing 1wt% polyvinyl alcohol were mixed and stirred for 10 minutes, and the obtained emulsion was cast on the substrate and pre-cured at 70°C for 20 minutes to obtain an opaque film material.
- the opaque film continued to open at 70°C.
- a transparent reversible dynamic macroporous elastomer polymer material was prepared.
- the reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, and the resulting emulsion was cast on the substrate and pre-cured at 70°C for 20 minutes to obtain an opaque film material, which was continued to be cured in an open environment at 70°C In 2 days, a transparent reversible dynamic macroporous elastomer polymer material was prepared.
- the reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3 g of an aqueous solution containing 1% polyvinyl alcohol were mixed and stirred for 30 minutes, and the obtained emulsion 1 was mixed.
- 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3 g of an aqueous solution containing 1% polyvinyl alcohol were mixed and stirred for 1 min, and the obtained emulsion 2 was mixed.
- the emulsion 1 and the emulsion 2 were mixed and stirred for 4 minutes to obtain a cured precursor.
- the curing precursor was cast on a substrate and pre-cured for 20 minutes in a closed environment at 70°C to obtain an opaque film material.
- the open mouth was cured in an open environment at 70°C for 2 days to obtain a transparent reversible dynamic macroporous elastomeric polymer material.
- a silicone precursor 10 g of A and 10 g of B and 0.05 g of a peryleneimide-based oil-soluble red organic pigment were uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3 g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, and the obtained emulsion was cast on the substrate and pre-cured for 20 minutes in a closed environment at 70°C to obtain an opaque film material; the opaque film material was continued at 70°C After curing in an open environment for 2 days, a transparent reversible dynamic macroporous elastomeric polymer material with red color was prepared.
- the colored reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- the reversible dynamic macroporous elastomeric polymer material with a functional pore surface prepared in this example is a transparent material.
- the reversible dynamic macroporous elastomer polymer material patterned under external stimulation is a transparent material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the organic silica gel precursor is poured on the substrate, and the polyvinyl alcohol aqueous solution is injected into the viscous precursor through a needle to form a fibrous water template that runs through the precursor, and then it is placed in an open environment at 70°C for 5 days to be cured.
- Transparent solid polymer material As shown in Figure 6, after applying tension (stimulus 1), a channel can be seen. On the contrary, by applying pressure (stimulus 2), the polymer material returns to its original shape.
- the channel reversible dynamic elastomer polymer material that opens and closes under external stimuli is a transparent material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, and the resulting emulsion was cast on the substrate and pre-cured in a closed environment at 70°C for 20 minutes, and then the pre-cured elastomer was stretched to 110 %, and then place it in an open environment at 70°C for 2 days to cure to obtain a 110% anisotropic transparent solid polymer material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, the resulting emulsion was poured on the substrate and pre-cured at 70°C for 20 minutes in a closed environment, and then the pre-cured elastomer was stretched to 170 %, and then placed it in an open environment at 70°C for 2 days to obtain a transparent solid polymer material with 170% anisotropy.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 3g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, and the resulting emulsion was cast on the substrate and pre-cured in a closed environment at 70°C for 20 minutes, and then the pre-cured elastomer was stretched to 250 %, and then place it in an open environment at 70° C. and cure for 2 days to prepare a 250% anisotropic transparent solid polymer material.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 1 g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, and the resulting emulsion was poured on the substrate and pre-cured in a closed environment at 70°C for 20 minutes, and then placed in an open environment at 70°C for curing 2 Tian, a transparent solid polymer material with a water content of 5 wt% was prepared.
- a silicone precursor 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- the silicone precursor and 20 g of 1% polyvinyl alcohol-containing aqueous solution were mixed and stirred for 30 minutes, and the resulting emulsion was poured on the substrate and pre-cured in a closed environment at 70°C for 20 minutes, and then placed in an open environment at 70°C for curing 2
- a transparent solid polymer material containing 50% by weight of water was prepared.
- 10 g of A and 10 g of B are uniformly mixed to obtain a silicone precursor.
- Mix 8 g of organic silicon precursor and 1 g of carbon black stir for 30 minutes to obtain a black liquid, brush the liquid on the tile, and place it at 70°C for 4 hours to cure to obtain the first layer.
- Mix 12g of silicone precursor and 30g of aqueous solution containing 1% polyvinyl alcohol for 30 minutes brush the obtained emulsion on the cured first layer sample, pre-curing at 70°C for 20 minutes in a closed environment, and then place it Cured in an open environment at 70°C for 2 days to obtain a double-layer material.
- the porous state is obtained by scraping, and the solid state is obtained by squeezing.
- the anisotropic reversible dynamic macroporous elastomeric polymer material prepared in this embodiment is a transparent material.
- Test Example 1 Responsiveness of mechanical force of reversible dynamic macroporous elastomeric polymer material
- the reversible dynamic macroporous elastomeric polymer material of the embodiment of the present invention is transformed from a solid state to a porous state under the action of tension; under the action of pressure, it transforms from a porous state to a solid state again to achieve Dynamically reversible.
- Test Example 2 Solvent responsiveness of reversible dynamic macroporous elastomeric polymer materials
- an elastomer material with a specific shape is formed in the solidified body, such as the chevron shown in Figure 5 and the one shown in Figure 6 Font.
- the initial solid state can be collapsed under tension to show the corresponding pattern, or the solvent can enter the large pores and swell to form the corresponding pattern.
- Test Example 3 The influence of template liquid content on pore structure
- Figures 7 and 8 when water is used as the template liquid, the elastomer polymer material prepared from the cured precursor with 15% water content is closed pores, and the elastomer polymer prepared from the cured precursor with 90% water content is Opening holes.
- Figure 9 is a macroporous elastomer polymer with a multi-layered pore structure obtained by mixing a variety of curing precursors with different water contents. It can be seen from Figure 10 that as the water content increases, the porosity increases.
- Test Example 4 The influence of different mechanical stimulation angles on optical performance
- the anisotropic reversible dynamic macroporous elastomer polymer material stretched to 250% has different light transmittance under the action of mechanical force at different angles.
- the tensile force direction is 0°, that is, when the tensile force is applied parallel to the surface of the material, with the continuous increase of the tensile force, the light transmittance hardly changes.
- the pulling force is inclined and is 45° or 90° with respect to the material surface, as the pulling force increases, the light transmittance gradually decreases, and the decrease is faster at 90° than at 45°.
- Test Example 5 The cooling and heating effect of reversible dynamic macroporous elastomer polymer material
- Figure 13 is a solid state, the temperature inside the material is significantly higher than the ambient air temperature, the material can let sunlight through, can effectively play a heating role;
- Figure 14 is a porous state, the coating The internal temperature is significantly lower than the atmospheric temperature, which can reflect sunlight and dissipate heat radiation, which plays a role in cooling.
- Test Example 7 Surface roughness of reversible dynamic macroporous elastomeric polymer material
- the surface roughness of the elastomeric polymer material changes.
- the contact angle is 108°
- the contact angle is 152°.
- the porous state is compared with The surface of the solid state is rougher.
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Abstract
Description
Claims (10)
- 一种可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,包括以下步骤:(1)将包含可聚合单体和交联剂的混合前体或者将可交联聚合前体与模板液混合,得到固化前体;其中,所述模板液为与所述混合前体不相容的挥发性溶液,或者为与所述可交联聚合前体不相容的挥发性溶液;(2)将所述固化前体施加至基底或模具中固化,制得可逆动态大孔弹性体聚合物材料。
- 根据权利要求1所述的可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,步骤(2)中固化过程是在开放环境中进行,固化温度为室温或不高于所述模板液的沸点温度。
- 根据权利要求1所述的可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,步骤(2)的固化过程包括以下步骤:(21)将所述固化前体施加至基底或模具中并且在所述模板液存在的条件下于密封环境中进行预固化,固化温度为室温或不高于所述模板液的沸点温度,得到预固化体;(22)将所述预固化体中的模板液的挥发性成分挥发去除,得到中间体;(23)将所述中间体进行终固化,固化温度为室温或低于200℃,制得可逆动态大孔弹性体聚合物材料。
- 根据权利要求1-3任一项所述的可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,所述可聚合单体为非挥发单体或沸点高于150℃的单体或两者混合物。
- 根据权利要求4所述的可逆动态大孔弹性体聚合物材料的制备方法,其 特征在于,所述可聚合单体为4-羟基丁基丙烯酸酯、丙烯酸异辛酯、聚(乙二醇)甲基醚丙烯酸酯、八甲基环四硅醚、甲基环戊二烯二聚体和双环戊二烯中的一种或多种组合;所述交联剂为1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,2-乙二醇二丙烯酸酯、1,2-乙二醇二甲基丙烯酸酯、聚(乙二醇)二丙烯酸酯和聚(乙二醇)二甲基丙烯酸酯中的一种或多种组合;所述模板液为水、聚乙烯醇水溶液、聚环氧乙烯水溶液、乙醇、异丙醇、***或正己烷。
- 根据权利要求4所述的可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,所述混合前体还包括引发剂和/或增稠剂。
- 根据权利要求1-3任一项所述的可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,所述可交联聚合前体为双端丙烯酸酯化的聚丙烯、双端丙烯酸酯化的聚四氢呋喃、双端丙烯酸酯化的聚丙烯、双端巯基化的聚丙烯、双端丙烯酸酯化的聚四氢呋喃和双端巯基化的聚四氢呋喃中的一种或多种组合,或者为有机硅胶;所述模板液为水、聚乙烯醇水溶液、聚(N-异丙基丙烯酰胺)水溶液、乙醇、异丙醇、***或正己烷。
- 根据权利要求7所述的可逆动态大孔弹性体聚合物材料的制备方法,其特征在于,所述可交联聚合前体还包括交联催化剂、自由基引发剂、油溶性有机颜料和表面活性剂中的一种或多种组合,所述交联催化剂为锡催化剂或铂催化剂。
- 权利要求1-8任一项所述的制备方法制备得到的可逆动态大孔弹性体聚 合物材料。
- 权利要求9所述的可逆动态大孔弹性体聚合物材料在制备刺激响应性聚合物材料中的应用。
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