CN110903508B - Stimulus-responsive polymer grafted wrinkled intelligent surface and preparation method and application thereof - Google Patents
Stimulus-responsive polymer grafted wrinkled intelligent surface and preparation method and application thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
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- C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—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
- C08J2433/14—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
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Abstract
The invention discloses a stimulus-responsive polymer grafted wrinkled intelligent surface and a preparation method and application thereof, and relates to the technical field of intelligent surfaces. The preparation method comprises the following steps: grafting a stimulus-responsive polymer to the surface of a sample with a wrinkled structure; wherein, the sample with the fold structure is obtained by heating and thermally shrinking a thermal shrinkage sheet with a metal film deposited on the surface, and the stimulus responsive polymer has a functional group capable of being grafted with the metal film. The application can conveniently graft the stimulus responsive polymer to the surface of the sample with the fold structure, and the preparation method is simple. The obtained wrinkled intelligent surface has switchable wettability and can realize directional transmission of acid-base liquid drops. The stimulus-responsive polymer grafted intelligent wrinkled surface can be widely applied to the fields of microfluidics, biomedicine, separation engineering and the like, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of intelligent surfaces, in particular to a stimulus-responsive polymer grafted wrinkled intelligent surface and a preparation method and application thereof.
Background
Smart surfaces refer to a class of surfaces that can act "intelligently" in response to external stimuli. The emergence of the functional material meets the requirement of people on material intellectualization, arouses wide interest in academic circles and industrial circles, and is one of hot spots of functional material research at present. The external environmental stimuli mainly include physical stimuli (such as heat, light, electricity, magnetism, force, and the like), chemical stimuli (such as pH, redox, gas, and the like), and biochemical stimuli (such as antigen, enzyme protein, glucose, and the like). Response behavior triggered by external stimuli is usually represented by drastic changes of surface macroscopic properties, including wettability, permeability, adhesiveness, adsorptivity, mechanical or optical characteristics and the like, and never represents corresponding functions of sensing, detection, self-repairing, self-driving and the like. Smart surfaces are currently used in many fields, such as microfluidics, where wettability-switchable surfaces are used to fabricate self-driven pumps, valves, etc. to achieve intelligent microfluidic transfer; in the aspect of biological medicine, the surface responding to temperature, ion concentration, protein and the like is beneficial to realizing the controllable entrapment and release of the medicine; in the field of separation science, the microporous membrane with switchable permeability can be applied to gas separation, sewage treatment, seawater desalination, water-oil separation and the like. In addition, the application of intelligent surfaces in environmental detection, tissue engineering, information processing and other aspects is also receiving wide attention.
The most common method for constructing intelligent surfaces is to graft various stimuli-responsive polymer materials onto the surfaces, i.e. the stimuli-responsiveness of the intelligent surfaces is achieved by relying on the surface-grafted polymers. After being stimulated by the outside, the molecular chain configuration or the functional group state of the responsive polymer is greatly changed, so that the properties of wettability, adhesiveness, light transmittance and the like of the surface are changed. Generally, since there is a limit in the grafting density of a polymer, the magnitude of change in surface properties is not large, that is, the switchability of a smart surface is not high. The performance switching amplitude of the intelligent surface can be enhanced to a certain extent by the surface roughening mode. For example, a response macromolecule is grafted on a flat surface, the switching amplitude of the surface contact angle is usually about 30 degrees, and the conversion of the surface wettability from super-hydrophilic to super-hydrophobic can be realized on a rough surface. Methods for producing rough surfaces include photolithography, etching, nanoparticle spraying, and template-assisted methods. The methods have complex process and high cost, or the prepared structure is single and the controllability is poor.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a stimulus-responsive polymer grafted wrinkled intelligent surface, which grafts a polymer to the surface of a wrinkled structure, so that the stimulus-responsive polymer grafted wrinkled intelligent surface with switchable wettability is obtained, and the whole preparation method is simple.
It is another object of the present invention to provide a stimuli-responsive polymer grafted wrinkled smart surface having switchable wettability.
It is yet another object of the present invention to provide the use of a stimulus-responsive polymer grafted wrinkled smart surface.
The invention is realized in the following way:
in a first aspect, embodiments provide a method for preparing a stimulus-responsive polymer grafted wrinkled smart surface, comprising:
grafting a stimulus-responsive polymer to the surface of the sample having a wrinkled structure;
the sample with the wrinkle structure is obtained by depositing a metal film on the surface of a heat-shrinkable sheet, heating the heat-shrinkable sheet deposited with the metal film for heat-shrinking, wherein the chain of the stimulus-responsive polymer contains a functional group capable of being grafted with the metal film.
In an optional embodiment, the metal film is made of Au, Ag, Al, Sn, or Ti; the functional group is a sulfhydryl group or an amino group;
Preferably, the metal film is Au, and the functional group is a thiol group.
In an alternative embodiment, the soaking time at the time of grafting is 12 to 18 hours;
preferably, after the grafting is finished, the method also comprises the steps of taking out the obtained product, cleaning and drying;
preferably, washing is performed with an ethanol solvent;
preferably, blow-drying is performed using nitrogen.
In an alternative embodiment, depositing the metal film on the surface of the heat-shrinkable sheet by magnetron sputtering;
preferably, the material of the heat shrink sheet is any one of PS, PE and PVC;
preferably, the sputtering power for magnetron sputtering deposition of the metal film is 80-120W;
preferably, the argon flow rate for magnetron sputtering deposition of the metal film is 20-30 sccm;
preferably, the sputtering time for magnetron sputtering deposition of the metal film is 50-400 s;
preferably, the heating temperature when heating for thermal shrinkage is 130-150 ℃;
preferably, the heating time for heat-shrinking is 25-35 min.
In an alternative embodiment, before the heat-shrinkable sheet deposited with the metal film is heated for heat-shrinking, a preset hollow-out pattern is formed on the surface of the metal film;
preferably, the preset hollowed-out pattern is a triangular array pattern;
Preferably, the triangle is an equilateral triangle,
preferably, in the preset hollow pattern, the length of the bottom side of each triangle is 100-;
preferably, in the preset hollowed-out pattern, the distance between any two adjacent rows of triangles is 50-150 μm, and the distance between any two adjacent rows of triangles is 50-150 μm.
In an alternative embodiment, before depositing the metal film, the preset hollow pattern is formed by covering a hollow template on the surface of the heat-shrinkable sheet and then sputtering; or,
after the metal film is deposited, the preset hollow pattern is formed on the metal film through laser direct writing.
In an alternative embodiment, the grafting is performed by soaking the sample having the wrinkle structure in a solution of the stimuli-responsive polymer;
the solution of the stimulus-responsive polymer is obtained by dissolving the stimulus-responsive polymer in an organic solvent, and the concentration of the stimulus-responsive polymer is 0.5 to 2 mmol/L;
preferably, the organic solvent is a mixture of one or more of ethanol, methanol and water.
In an alternative embodiment, the method for preparing the stimuli-responsive polymer comprises: adding a monomer, an initiator and a chain transfer agent into a reaction solvent to carry out RAFT polymerization;
Preferably, the monomer comprises a mixture of one or more of diethylaminoethyl methacrylate, acrylic acid, N-isopropylacrylamide, a monomer containing a spiropyran functionality, and a monomer containing an azobenzene functionality;
preferably, the initiator is AIBN;
preferably, the chain transfer agent is a dithioester derivative or a trithioester derivative;
preferably, the chain transfer agent is 4-cyanovaleric acid dithiobenzoic acid;
preferably, the reaction solvent is a mixture of one or more of tetrahydrofuran, dioxane, dichloromethane and methanol;
preferably, the reaction temperature at which the RAFT polymerisation reaction is carried out is from 70 to 80 ℃;
preferably, the reaction time when performing the RAFT polymerisation reaction is from 6 to 12 h;
preferably, before the RAFT polymerization reaction is carried out, oxygen is removed from the reaction system, and oxygen is isolated and stirred during the reaction process;
preferably, after completion of the RAFT polymerisation reaction, air is contacted for quenching, followed by post-precipitation purification of the reaction solution.
In a second aspect, embodiments provide a stimulus-responsive polymer grafted wrinkled smart surface, which is prepared by the method for preparing a stimulus-responsive polymer grafted wrinkled smart surface according to any one of the preceding embodiments.
In a third aspect, embodiments provide the use of a stimuli-responsive polymer grafted pleated smart surface as described in the previous embodiments in microfluidic smart transport, controlled entrapment and release of drugs, gas separation, wastewater treatment, desalination, water-oil separation, environmental detection, tissue engineering, or information processing.
The invention has the following beneficial effects:
according to the application, the stimulation responsive polymer is grafted to the surface of a sample with a folded structure through the matching of the metal film and the functional group capable of being grafted with the metal film, and the preparation method is simple. Compared with the method for grafting the stimulus-responsive polymer to the flat surface, the prepared wrinkle intelligent surface grafted by the stimulus-responsive polymer has the advantages that the wrinkle structure can enhance the performance switching range of the intelligent surface, the transition of the surface wettability from super-hydrophilic to super-hydrophobic can be realized, the wrinkle intelligent surface constructed by the method has switchable wettability, and the directional transmission of acid-base liquid drops can be realized. The stimulus-responsive polymer grafted intelligent wrinkled surface can be widely applied to the fields of intelligent microfluid transmission, controllable entrapment and release of medicines, gas separation, sewage treatment, seawater desalination, water-oil separation, environmental detection, tissue engineering or information processing and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a thermal shrinking process provided in example 1 of the present application;
FIG. 2 is a schematic view of a pleat structure formed after heat shrinking as provided in example 1 of the present application;
FIG. 3 is a schematic view of a wrinkle structure formed after heat shrinking as provided in example 2 of the present application;
FIG. 4 is a schematic view of a pleat structure formed after heat shrinking as provided in example 3 of the present application;
FIG. 5 is a schematic view of a pleat structure formed after heat shrinking as provided in example 4 of the present application;
FIG. 6 is a graph showing the contact angle test results of example 1 and comparative example 1 in the first experimental example of the present application;
FIG. 7 is a graph showing the results of measurements of contact angles at low temperature (20 ℃) and high temperature (50 ℃) of the smart surfaces obtained in example 5 and comparative example 4 of the second experimental example of the present application;
Fig. 8 is a schematic structural view of a stencil used in embodiment 6 of the present application;
FIG. 9 is a schematic structural diagram of a triangular array pattern of a heat-shrinkable sheet deposited with a patterned metal film on a surface after heat-shrinking, obtained in example 6 of the present application;
fig. 10 is a graph showing the results of the dynamic contact angle test of acidic and basic droplets on the smart surface prepared in example 6 in the third experimental example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of a stimulus-responsive polymer grafted wrinkled intelligent surface, which comprises the following steps:
and S1, grafting a stimulus responsive polymer to the surface of the sample with the corrugated structure.
In the present application, a stimulus-responsive polymer having a specific functional group is selected and combined with a corrugated structure having a specific metal film, thereby grafting the stimulus-responsive polymer to the corrugated structure. The fold structure has larger surface roughness, and the performance switching amplitude of the intelligent surface can be enhanced by grafting the stimulus responsive polymer on the surface of the fold structure.
Wherein the metal film is Au, Ag, Al, Sn or Ti; the functional group is sulfhydryl or amino; preferably, the metal film is Au and the functional group is a thiol group.
Next, the present application will be described by taking, as an example, the preparation of a stimuli-responsive polymer having a thiol group as a terminal group and a wrinkled structure having an Au thin film.
Specifically, step S1 includes the steps of:
s101, preparing a stimulus-responsive polymer with stimulus responsiveness.
Deoxidizing a reaction system, adding a monomer, an initiator and a chain transfer agent into a reaction solvent to carry out RAFT polymerization, isolating oxygen and stirring in the reaction process, after the RAFT polymerization is finished, contacting air to quench, precipitating a reaction solution, and purifying.
Among them, the term "RAFT Polymerization" is short for Reversible Addition-Fragmentation Chain Transfer Polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization), which is one of living/Controlled Radical Polymerization (CRP).
Specifically, the method for purifying the reaction solution after precipitation comprises the following steps: the reaction solution is precipitated in an organic solvent (including but not limited to one or more of n-hexane, diethyl ether) and then the precipitate is filtered off and purified by vacuum extraction. The crude product is a polymer with dithio (or trithio) ester at the end group. Then adding the crude product and a reducing agent into a solvent together for reaction. After the reaction is finished, precipitating the mixed solution in an organic solvent (including but not limited to one or more of n-hexane and diethyl ether), filtering out the precipitate, and purifying in vacuum by pumping to obtain the stimulation responsive polymer with the end group of sulfhydryl. Reducing agents in the present application include, but are not limited to, hexylamine, threitol (DTT), NaH 4And the like, including but not limited to tetrahydrofuran, dioxane, methylene chloride, methanol, and the like.
Preferably, the monomer comprises a mixture of one or more of diethylaminoethyl methacrylate (DEAEMA), acrylic acid, N-isopropylacrylamide (NIPAM), a spiropyran-functional group-containing monomer, and an azobenzene-functional group-containing monomer; preferably, the initiator is AIBN; preferably, the chain transfer agent is a dithioester derivative or a trithioester derivative; in the present application, by selecting a suitable metal film and a functional group to which the metal film can be grafted in advance and then selecting a suitable chain transfer agent according to the functional group, since the product to be prepared is a stimuli-responsive polymer whose terminal group is a mercapto group in the present application, the chain transfer agent is a dithioester derivative or a trithioester derivative in the present application, and specifically in the present embodiment, the chain transfer agent is 4-cyanovaleric acid dithiobenzoic acid (CPADB). .
Preferably, the reaction solvent is a mixture of one or more of tetrahydrofuran, dioxane, dichloromethane and methanol; preferably, the reaction temperature when performing RAFT polymerisation is from 70 to 80 ℃; preferably, the reaction time when performing RAFT polymerisation is from 6 to 12 hours.
S102, preparing a sample with a wrinkle structure.
Wrinkles, a common surface destabilization phenomenon, have been gradually developed as a potential surface structure fabrication method. Generally, when a two-layer film system is subjected to compressive stress, a hard surface layer is subjected to rigid bending, a soft substrate is subjected to flexible deformation, and the whole body forms a corrugated structure. The corrugated structure is generally disordered, isotropic, but with a fixed period. Compared with the traditional processing method, the corrugation technology has the advantages of relatively simple process, quick forming and large-area manufacturing; the process does not involve etching of materials, so that the method is safer and more environment-friendly; it is widely applicable to various material systems and can be used for constructing various functional structures and devices.
In the application, a double-layer structure (a heat-shrinkable sheet deposited with a metal film) is obtained by depositing the metal film on the surface of the heat-shrinkable sheet, and the sample with the folded structure is obtained after the heat-shrinkable sheet deposited with the metal film is heated for heat shrinkage.
Specifically, the material of the heat shrink sheet is any one of PS, PE, and PVC.
There are various ways of depositing the metal film on the surface of the heat shrinkable sheet, including but not limited to magnetron sputtering deposition, electron beam evaporation or thermal evaporation, and the like, and in the present application, the metal film is preferably deposited by a sputtering method The metal film is deposited by magnetron sputtering. The parameters of the magnetron sputtering deposition metal film comprise: the sputtering power is 80-120W, the argon flow rate is 20-30sccm, and the sputtering rate is 1.0-1.2nm s-1And a sputtering time of 50 to 400 s.
And heating the obtained heat-shrinkable sheet deposited with the metal film at the temperature of 130-150 ℃ for 25-35min for heat-shrinking to form a corrugated structure.
It is worth noting that, in the application, before the heat-shrinkable sheet deposited with the metal film is heated for heat-shrinking, a preset hollow-out pattern is formed on the surface of the metal film; the preset hollow pattern can be formed in various ways, for example, before the metal film is deposited, the surface of the heat-shrinkable sheet is covered with a hollow template and then sputtered to form the preset hollow pattern; or after the metal film is deposited, the preset hollow-out pattern is formed on the metal film through laser direct writing.
Specifically, the predetermined hollow pattern is a triangular array pattern. Preferably, the triangle is an equilateral triangle, in the preset hollow pattern, the length of the bottom side of each triangle is 100-; the distance between any two adjacent rows of triangles is 50-150 μm, and the distance between any two adjacent rows of triangles is 50-150 μm.
According to the method, the triangular array hollowed-out pattern is formed, and the surface of the prepared fold structure is provided with the asymmetric triangular array pattern. In this application, the pointed direction of the apex angle of triangle-shaped on the definition fretwork template is the positive direction, then the pattern of Au fold structure points to the positive direction on the product, and the remainder is the exposed substrate surface, and its pattern points to the negative direction, as shown in fig. 9. Based on the specific hollow pattern, the stimulus-responsive polymer grafted wrinkled intelligent surface provided by the application has different directional transmission characteristics for acid/alkaline liquid. Specifically, if the acidic liquid is continuously dropped on the surface, the liquid drop will continuously spread toward the negative direction, and the interface of the liquid drop is pinned in the positive direction; conversely, if an alkaline liquid is continuously dropped on the surface, the liquid droplet is continuously spread toward the positive direction and pinned in the negative direction. The directional transport of liquid over a stimulus responsive polymer grafted corrugated smart surface is shown in figure 10.
S103, grafting a stimulus-responsive polymer to the surface of the sample with the wrinkle structure.
The stimulus-responsive polymer prepared in step S101 is dissolved in an organic solvent (including but not limited to a mixture of one or more of ethanol, methanol, and water) to prepare a stimulus-responsive polymer solution having a concentration of the stimulus-responsive polymer of 0.5 to 2 mmol/L.
And (4) soaking the folded structure prepared in the step (S102) in a stimulus-responsive polymer solution for grafting, wherein the grafting time is 12-18h, and after the grafting is finished, taking out a grafted product, cleaning and drying. Specifically, the grafted product dosage form is cleaned by using an ethanol solution, and the intelligent wrinkled surface grafted by the stimuli-responsive polymer can be obtained by blowing dry by using nitrogen.
The stimulus-responsive polymer grafted wrinkled intelligent surface has switchable surface wettability and can directionally transmit.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a stimulus-responsive polymer grafted wrinkled smart surface (PDEAEMA-Au/PS wrinkled surface) with switchable surface wettability, and the preparation method comprises the following steps:
s101, preparing a stimulus-responsive polymer with stimulus responsiveness.
The reaction system was deoxygenated, and 5.91g of monomer (DEAEMA), 0.013g of initiator (AIBN), and 0.089g of chain transfer agent (CPADB) were added to 30mL of tetrahydrofuran, and the reaction was stirred at 70 ℃ with exclusion of oxygen for 6 hours.
After completion of the polymerization reaction, the reaction solution was precipitated in 250mL of n-hexane, and then the precipitate was filtered off and purified by suction in vacuo. The crude product was 3.12g of a polymer having dithioester at the terminal.
Then 3.12g of the crude product were added to 30mL of dichloromethane together with 0.494g of hexylamine and 8.30mg of Dithiothreitol (DTT), and the reaction was stirred at room temperature for 12 hours while isolating oxygen. After the reaction was completed, the mixed solution was precipitated in 250mL of n-hexane, and the precipitate was filtered off and purified by vacuum suction to obtain 1.89g of a stimuli-responsive polymer having a mercapto group as a terminal group.
S102, preparing a sample with a wrinkle structure.
And carrying out sputtering deposition on the Au film on the surface of the PS thermal shrinkage sheet by utilizing magnetron sputtering. The parameters for magnetron sputtering deposition of the metal film comprise: the sputtering power was 100W, the argon flow rate was 25sccm, and the sputtering time was 150 s. The thickness of the sputtered Au film under the condition is about 16.5 nm.
After obtaining the heat shrinkable sheet deposited with the metal film, the sheet was heated at 140 ℃ for 30min for heat shrinkage (see fig. 1), and it can be seen from fig. 1 that the area of the sample before and after the heat shrinkage process was about 1/4. The heat shrinking process generates a large amount of strain, so that the surface is wrinkled (see fig. 2). It can be seen from fig. 2 that the corrugation structure is isotropic under this condition, with a corrugation period of about 290 nm.
S103, grafting a stimulus-responsive polymer to the surface of the sample with the wrinkle structure.
The stimulus-responsive polymer prepared in step S101 was dissolved in ethanol to prepare a stimulus-responsive polymer solution having a stimulus-responsive polymer concentration of 1 mmol/L.
And (2) soaking the wrinkled structure prepared in the step (S102) in a stimulus-responsive polymer solution for grafting, wherein the grafting time is 12 hours, taking out the grafted product after grafting is finished, cleaning the grafted product by using an ethanol solution, and drying by using nitrogen to obtain the stimulus-responsive polymer grafted wrinkled intelligent surface.
Example 2
The embodiment provides a wrinkled intelligent surface (PDEAEMA-Au/PS wrinkled surface) grafted by a stimulus-responsive polymer, the preparation method is basically the same as that of embodiment 1, except that in step S102 of the embodiment, the sputtering time of the Au thin film sputtered on the surface of the PS heat-shrinkable sheet is changed to 50S, and under the condition, the thickness of the Au thin film is about 5.5 nm; accordingly, the resulting wrinkled surface has a wrinkle period of about 130nm as shown in FIG. 3.
Example 3
The embodiment provides a wrinkled intelligent surface (PDEAEMA-Au/PS wrinkled surface) grafted by a stimulus-responsive polymer, the preparation method is basically the same as that of the embodiment 1, except that in the step S102 of the embodiment, the sputtering time of the Au thin film sputtered on the surface of the PS heat shrinkable sheet is changed to 250S, and the thickness of the Au thin film is about 27.5nm under the condition; accordingly, the resulting wrinkled surface had a wrinkle period of about 520nm as shown in FIG. 4.
Example 4
The embodiment provides a wrinkled intelligent surface (PDEAEMA-Au/PS wrinkled surface) grafted by stimulus-responsive polymer, the preparation method is basically the same as that of embodiment 1, except that in step S102 of the embodiment, the sputtering time of the Au thin film sputtered on the surface of the PS heat shrinkable sheet is changed to 400S, and under the condition, the thickness of the Au thin film is about 44 nm; accordingly, the resulting wrinkled surface had a wrinkle period of about 840nm as shown in FIG. 5.
Comparative example 1
The heat-shrinking step in example 1 was omitted to form a planar structure of Au/PS, and a stimulus-responsive Polymer (PDEAEMA) was grafted to the surface of the planar structure of Au/PS according to the grafting step in example 1.
Comparative example 2
The grafting step in example 1 was omitted, and the Au/PS wrinkled surface without grafted polymer was obtained by the sputtering and thermal shrinkage process in example 1.
Comparative example 3
Omitting the metallic Au sputtering step in example 1, no wrinkled structure was generated on the heat-shrunk PS surface. The heat-shrinkable PS film was soaked in the stimulus-responsive polymer solution for 12h according to the grafting procedure in example 1.
The first experimental example:
the acid/base contact angles of the smart surfaces obtained in examples 1 to 4 and comparative examples 1 to 3 were measured, and the results of the measurements are shown in fig. 6 and table 1:
TABLE 1 acid/base contact Angle results for smart surfaces
From the results it can be seen that:
1) the pH responsiveness of the intelligent surface wettability comes from the surface grafted macromolecules. For comparative example 2, the grafting process was omitted and the surface had no pH response; in contrast, comparative example 3 has no pH response characteristics because the surface has no Au thin film, so that the polymer cannot be grafted on the surface of the sample.
2) The wrinkled surface can greatly enhance the stimulus responsiveness of the polymer grafted surface. In comparative example 1, a stimulus responsive polymer is grafted on a flat Au/PS surface, and a pH responsive surface can also be obtained, but the switching amplitude of the contact angle is small and is only about 30 degrees; in examples 1 to 4, the contact angle switching amplitude of the pH-responsive surface was greatly increased to 100 ° or more after the introduction of the corrugated structure. The specific results are shown in FIG. 6.
3) In the embodiments 1 to 4, the shape and the structural parameters of the folds are adjusted through the sputtering time, so that a certain adjusting effect on the contact angle switching range of the intelligent surface can be achieved; in example 1, the sample having the best pH response performance in terms of the contact angle switching range was set to have a sputtering time of 150 seconds.
Example 5:
This example provides a stimulus-responsive polymer grafted wrinkled smart surface (PNIPAM-Au/PS wrinkled surface), which is prepared in a similar manner to example 1, including:
s101, preparing a stimulus-responsive polymer with stimulus responsiveness.
The reaction system was deoxygenated and 5.86g of monomer (NIPAM), 0.021g of initiator (AIBN) and 0.145g of chain transfer agent (CPADB) were added to 30mL of tetrahydrofuran, and the reaction was stirred at 70 ℃ with exclusion of oxygen for 6 hours.
After the polymerization was completed, the reaction solution was precipitated in 250mL of n-hexane, and then the precipitate was filtered off and purified by suction in vacuo. The crude product was 3.72g of a polymer having dithioester at the end group.
Then 3.72g of the crude product were added together with 0.649g of hexylamine and 12.4mg of Dithiothreitol (DTT) to 30mL of dichloromethane, and the reaction was stirred at room temperature with exclusion of oxygen for 12 hours. After the reaction was completed, the mixed solution was precipitated in 250mL of n-hexane, and the precipitate was filtered off and purified by vacuum suction to obtain 2.17g of a stimuli-responsive polymer having a mercapto group as a terminal group.
S102, preparing a sample with a wrinkle structure.
This corresponds to S102 in example 1.
Au thin films are sputtered on the PS heat shrinkage sheets, and Au/PS folding structures are prepared through the heat shrinkage process.
S103, grafting a stimulus-responsive polymer to the surface of the sample with the wrinkle structure.
This corresponds to S103 in example 1.
The stimulus-responsive polymer prepared in step S101 was dissolved in ethanol to prepare a stimulus-responsive polymer solution having a stimulus-responsive polymer concentration of 1 mmol/L.
And (3) soaking the wrinkled structure prepared in the step (S102) in a stimulus-responsive polymer solution for grafting, wherein the grafting time is 12h, taking out the grafted product after grafting is finished, cleaning the grafted product by using an ethanol solution, and drying by using nitrogen to obtain the stimulus-responsive polymer grafted wrinkled intelligent surface.
Comparative example 4:
the heat shrinking step in example 5 was omitted to form a planar structure of Au/PS, and a stimuli-responsive polymer (PNIPAM) was grafted to the surface of the planar structure of Au/PS according to the grafting step in example 5.
Experiment example two:
the contact angles at low temperature (20 ℃) and high temperature (50 ℃) of the smart surfaces obtained in example 5 and comparative example 4 were measured, and the results are shown in fig. 7 and table 2:
TABLE 2 acid/base contact Angle results for smart surfaces
| Examples of the invention | Water contact angle at 20 DEG C | Water contact angle of 50 deg.C | Difference in contact angle |
| Example 5 | 22.1° | 120.1° | 98.0° |
| Comparative example 4 | 74.1° | 85.0° | 10.9 |
From the results it can be seen that:
the stimulus responsiveness of the wrinkled surface to the polymeric grafted surface is also applicable to the temperature responsive PNIPAM grafted surface. In comparative example 4, a stimulus responsive polymer PNIPAM is grafted on a flat Au/PS surface, so that a temperature responsive surface can be obtained, and the switching amplitude of contact angles at different temperatures is small and is only about 10 degrees; in example 5, the contact angle switching range of the temperature-responsive surface was greatly increased to about 100 ° after the introduction of the wrinkle structure. The specific results are shown in FIG. 7.
Example 6:
the embodiment provides a stimulus-responsive polymer grafted wrinkled intelligent surface (PDEAEMA-Au/PS wrinkled surface) with switchable droplet directional transmission characteristics, and the preparation method introduces an asymmetric pattern on the basis of embodiment 1, and comprises the following specific steps:
s101, preparing a stimulus-responsive polymer with stimulus responsiveness.
This corresponds to S101 in example 1.
S102, preparing a sample with an asymmetric patterned corrugated structure.
And sputtering and depositing an Au film on the surface of the PS heat-shrinkable sheet by utilizing magnetron sputtering. And covering the surface of the sample with a hollow template with a specific pattern during sputtering. The specific pattern of the hollow template is shown in figure 8. In the hollow template, the length of the side of the bottom edge of each triangle is 1.0mm, and the height of each triangle is 2.0 mm; the distance between any two adjacent rows of triangles and the distance between any two adjacent rows of triangles are both 0.3 mm.
The parameters of the magnetron sputtering deposition metal film comprise: the sputtering power was 100W, the argon flow rate was 25sccm, and the sputtering time was 150 s. The thickness of the sputtered Au film under the condition is about 16.5 nm.
And heating the obtained heat-shrinkable sheet deposited with the patterned metal film at the temperature of 140 ℃ for 30min for heat-shrinking, wherein a large amount of strain is generated in the heat-shrinking process, so that a wrinkle structure is formed on the surface of the Au layer at the triangular part. The area of the sample before and after the heat shrinking process was approximately changed to 1/4. Accordingly, the lateral dimension of the triangular array pattern of the surface also shrinks to the original 1/2. Specifically, in the surface pattern after heat shrinking, the side length of the base of each triangle is about 500 μm, and the height of each triangle is about 1000 μm; the pitch between any two adjacent rows of triangles and the pitch between any two adjacent rows of triangles are both about 150 μm. As shown in fig. 9.
S103, grafting a stimulus-responsive polymer to the surface of the sample with the wrinkle structure.
This corresponds to S103 in example 1. Due to the interaction between Au and sulfhydryl (-SH), the stimulus responsive polymer is only grafted on the Au fold surface of the triangle part.
Experiment example three:
the smart surface prepared in example 6 was subjected to a dynamic contact angle test of acidic and basic droplets. The results are shown in FIG. 10.
As can be seen from the results of fig. 10:
when the acidic liquid drop is continuously dripped on the surface of the sample, the liquid drop can continuously spread towards the left side, namely the liquid interface on the left side continuously moves, and the liquid interface on the right side is pinned; conversely, when an alkaline droplet is added, the droplet spreads to the right, i.e., the liquid interface on the right moves, while the liquid interface on the left is pinned.
Comparative example 5
The triangular array hollowed template used in example 6 was replaced with a circular hole array hollowed template, each circular hole having a diameter of 150 μm and the distance between any two circular holes being 100 μm. Correspondingly, the diameter of the circular wrinkled area on the surface of the sample after heat shrinkage is 75 μm, and the interval between areas is 50 μm.
Experimental example four:
the smart surface prepared in comparative example 5 was subjected to a dynamic contact angle test of acidic and basic droplets. Regardless of whether acidic or basic droplets are dropped on the surface of the sample, the spreading degree of the liquid towards each direction is consistent, and no obvious difference of the moving speed exists in the liquid interface in each direction. This phenomenon illustrates that a necessary condition for creating directional droplet transport is to build an asymmetric pattern on the surface (e.g. a triangular array), whereas for an isotropic symmetric pattern (a circular array), the spreading behavior of the liquid is also isotropic.
In summary, the sample with the wrinkled structure is soaked in the stimuli-responsive polymer solution, the stimuli-responsive polymer is grafted to the surface of the sample with the wrinkled structure through the matching of the metal film and the functional group capable of being grafted with the metal film, and the whole preparation method is simple. Compared with the method for grafting the stimulus-responsive polymer to the flat surface, the prepared fold intelligent surface grafted by the stimulus-responsive polymer has the advantages that the fold structure can enhance the performance switching range of the intelligent surface, the transition of the surface wettability from super-hydrophilic to super-hydrophobic can be realized, and the fold intelligent surface constructed by the method has switchable wettability and can induce the directional transmission of different acid-base liquid drops. The stimulus-responsive polymer grafted intelligent wrinkled surface can be widely applied to the fields of intelligent microfluid transmission, controllable entrapment and release of medicines, gas separation, sewage treatment, seawater desalination, water-oil separation, environmental detection, tissue engineering or information processing and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (34)
1. A method for preparing a stimulus-responsive polymer grafted wrinkled intelligent surface is characterized by comprising the following steps:
grafting a stimulus-responsive polymer to the surface of a sample with a wrinkled structure;
the sample with the wrinkle structure is obtained by depositing a metal film on the surface of a heat-shrinkable sheet, heating the heat-shrinkable sheet deposited with the metal film for heat-shrinking, wherein the chain of the stimulus-responsive polymer contains a functional group capable of being grafted with the metal film.
2. The method for preparing the stimulus-responsive polymer-grafted wrinkled intelligent surface according to claim 1, wherein the metal film is made of Au, Ag, Al, Sn or Ti; the functional group is a mercapto group or an amine group.
3. The method of claim 2, wherein the metal film is Au and the functional group is thiol.
4. The method of claim 1, wherein the soaking time during grafting is 12-18 h.
5. The method for preparing a stimulus-responsive polymer grafted wrinkled smart surface according to claim 4, wherein the grafting is completed, and further comprising taking out the obtained product, washing and drying.
6. The method of claim 5, wherein the cleaning is performed with ethanol solvent.
7. The method of claim 5, wherein the drying is performed with nitrogen.
8. The method of claim 1, wherein the metal film is deposited on the surface of the heat shrink sheet by magnetron sputtering.
9. The method of claim 8, wherein the material of the heat shrink sheet is any one of PS, PE and PVC.
10. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 8, wherein the sputtering power for magnetron sputtering deposition of the metal film is 80-120W.
11. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 8, wherein the argon gas flow rate for magnetron sputtering deposition of the metal film is 20-30 sccm.
12. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 8, wherein the sputtering time for magnetron sputtering deposition of the metal film is 50-400 s.
13. The method for preparing the stimulus-responsive polymer grafted wrinkled smart surface as claimed in claim 1, wherein the heating temperature for heat shrinking is 130-150 ℃.
14. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 1, wherein the heating time for the heat shrinking is 25-35 min.
15. The method for preparing a stimulus-responsive polymer grafted wrinkled smart surface according to claim 1, wherein a preset hollowed-out pattern is formed on the surface of the metal film before the heat shrinkable sheet deposited with the metal film is heated for heat shrinking.
16. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 15, wherein the predetermined hollowed-out pattern is a triangular array pattern.
17. The method of claim 16, wherein the triangle is an equilateral triangle.
18. The method as claimed in claim 16, wherein the predetermined hollow pattern has a length of the bottom side of each triangle of 100-500 μm and a height of each triangle of 200-1000 μm.
19. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 16, wherein in the preset hollowed-out pattern, the distance between any two adjacent rows of triangles is 50-150 μm, and the distance between any two adjacent rows of triangles is 50-150 μm.
20. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 15, wherein before depositing the metal film, the surface of the heat-shrinkable sheet is covered with a hollowed-out template and then sputtered to form the predetermined hollowed-out pattern; or,
after the metal film is deposited, the preset hollow pattern is formed on the metal film through laser direct writing.
21. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 1, wherein the grafting is performed by immersing the sample having a wrinkled structure in a solution of the stimulus-responsive polymer;
the solution of the stimulus-responsive polymer is obtained by dissolving the stimulus-responsive polymer in an organic solvent, and the concentration of the stimulus-responsive polymer is 0.5 to 2 mmol/L.
22. The method of claim 21, wherein the organic solvent is a mixture of one or more of ethanol and methanol.
23. The method for preparing a stimulus-responsive polymer-grafted wrinkled smart surface according to claim 1, wherein the method for preparing the stimulus-responsive polymer comprises: adding a monomer, an initiator and a chain transfer agent into a reaction solvent to carry out RAFT polymerization.
24. The method of claim 23, wherein the monomer comprises one or more of diethylaminoethyl methacrylate, acrylic acid, N-isopropylacrylamide, a monomer with a spiropyran functionality, and a monomer with an azobenzene functionality.
25. The method of claim 23, wherein the initiator is AIBN.
26. The method of claim 23, wherein the chain transfer agent is a dithioester derivative or a trithioester derivative.
27. The method of claim 26, wherein the chain transfer agent is 4-cyanovaleric acid dithiobenzoic acid.
28. The method of claim 23, wherein the reaction solvent is one or more of tetrahydrofuran, dioxane, dichloromethane, and methanol.
29. The method of claim 23, wherein the RAFT polymerization is carried out at a reaction temperature of 70-80 ℃.
30. The method of claim 23, wherein the RAFT polymerization is carried out for a reaction time of 6-12 hours.
31. The method for preparing a stimulus-responsive polymer grafted wrinkled smart surface according to claim 23, wherein oxygen is removed from the reaction system before the RAFT polymerization reaction is performed, and the reaction system is stirred while oxygen is isolated.
32. The method of claim 23, wherein the RAFT polymerization is completed and then quenched by exposure to air, followed by post-precipitation purification of the reaction solution.
33. A stimuli-responsive polymer-grafted, wrinkled smart surface, prepared by the method of any one of claims 1-32, wherein the method comprises the step of preparing the stimuli-responsive polymer-grafted, wrinkled smart surface.
34. The use of the stimulus-responsive polymer-grafted pleated smart surface of claim 33 in microfluidic smart transport, controlled entrapment and release of drugs, gas separation, sewage treatment, seawater desalination, water-oil separation, environmental detection, tissue engineering, or information processing.
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