CN108329645B - Hybrid material with ultraviolet light induced gradient structure, preparation method and application of hybrid material in responsive shape transformation - Google Patents
Hybrid material with ultraviolet light induced gradient structure, preparation method and application of hybrid material in responsive shape transformation Download PDFInfo
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- CN108329645B CN108329645B CN201810103482.1A CN201810103482A CN108329645B CN 108329645 B CN108329645 B CN 108329645B CN 201810103482 A CN201810103482 A CN 201810103482A CN 108329645 B CN108329645 B CN 108329645B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- 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
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a hybrid material with an ultraviolet light induced gradient structure, a preparation method and application thereof in responsive shape transformation. The hybrid material is a membrane material formed by compounding an elastomer material grafted by a photosensitive group and a carbon nano material; the photosensitive group is a group capable of performing photodimerization reaction, and the substrate of the elastomer material is an elastomer containing isolated double bonds. The invention utilizes the characteristic of the carbon nano material of absorbing light, during photocrosslinking, the light intensity at different depths in the material is adjusted, the control of the dimerization rate of photodimerization groups at different depths and the crosslinking density of the material is realized, and further the film material has a gradient structure in the vertical direction, and the formation of the gradient structure realizes the transformation of various shapes under the condition of external stimulation (such as temperature, solvent, infrared light and the like); meanwhile, the photoinduced gradient structure is reversible and can be erased by heating or ultraviolet irradiation below 300nm to restore to the original linear structure.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation and application, and particularly relates to a hybrid material with an ultraviolet light induced gradient structure, a preparation method and application thereof in responsive shape transformation.
Background
At present, the responsive shape transformation of the material is a hot spot direction of research, and the unbalanced structural material shows great advantages in the research of the responsive shape transformation. The existence of the unbalanced structure enables the shape of the unbalanced structure to be changed more variously and designably according to regulation when the response behavior occurs. However, in the current research, the preparation of the unbalanced structure material is mostly focused on two main methods, namely a layer-by-layer structure and a liquid crystal polymer. In the preparation process of the layer-by-layer structure, two different polymers are required to be selected and bonded together, so that a double-layer structure with different properties is formed. When the double-layer structure is stimulated by the outside, the shape of the material is changed due to the difference of internal stress. However, this method has the disadvantage that the interaction between the two polymers is in a suitable range so that the two can be effectively bonded together. The bilayer structure is also prone to separation during use. The liquid crystal polymer material obtains the unbalanced structure by introducing a liquid crystal structure into a material system and realizing the preparation of the unbalanced structure by utilizing the crystal phase transformation of liquid crystal and the regional difference of the orientation of the liquid crystal structure. However, this method mostly requires complex synthesis process and specific liquid crystal orientation conditions, and the process is complex and harsh, so it is not suitable for wide-scale popularization and application.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a recyclable hybrid material with an ultraviolet light induced gradient structure, a preparation method and application thereof in responsive shape transformation. The invention can simply and quickly obtain the hybrid material with the photoinduced unbalanced gradient structure, and the hybrid material with the gradient structure can realize various shape changes under the condition of external stimulation (such as temperature, solvent, infrared light and the like).
In the invention, the photodimerization group in the elastomer material grafted by the photosensitive group can carry out self-crosslinking reaction under the condition of ultraviolet illumination, and molecular chains in the elastomer are partially locked by utilizing the self-crosslinking reaction. The addition of the carbon nano material can adjust the light intensity at different depths in the material during photocrosslinking, thereby realizing the control of the dimerization rate of the photodimerization groups at different depths and the crosslinking density of the material, and further obtaining the membrane material with a gradient structure in the vertical direction. The heterogeneity of the material structure enables the material to generate three-dimensional shape transformation under the condition of external stimulation. And the membrane material with the gradient structure is applied to the research in the field of shape transformation. Compared with a thermal control structure, the forming controllability of the optical control structure is stronger, the optical control structure can be designed as required, and further more various shape changes can be obtained. And due to the reversibility of self-crosslinking reaction, the process is reversible, the structure of the hybrid membrane material can be converted between a balanced structure and a gradient structure under the condition of ultraviolet light illumination of less than 300nm or high temperature, the shape conversion is also reversible, and the hybrid membrane material can be repeatedly recycled.
The technical scheme of the invention is specifically explained as follows.
The invention provides a hybrid material with an ultraviolet light induced gradient structure, which is a membrane material formed by compounding an elastomer material grafted by a photosensitive group and a carbon nano material; wherein: the photosensitive group is a group for generating photodimerization reaction, and the substrate of the elastomer material is an elastomer containing isolated double bonds.
In the invention, the mass ratio of the elastomer material grafted by the photosensitive group to the carbon nano material is 1:0.001-1: 0.2.
In the invention, the photosensitive group is selected from any one or more of coumarin group, anthracene group, chalcone group or cinnamate group; the matrix of the elastomer material is selected from any one of butadiene rubber, SBS, SIS, SIBS, nitrile rubber, styrene butadiene rubber, natural rubber or EPDM.
In the invention, the photosensitive group grafted elastomer is prepared by the following steps:
(1) dissolving an elastomer containing isolated double bonds and a mercapto carboxyl compound in an organic solvent, uniformly stirring, adding a photoinitiator, and carrying out mercapto-alkene click reaction under the condition of ultraviolet illumination to obtain a modified elastomer after carboxyl grafting; wherein: the mercapto carboxyl compound is a compound which simultaneously contains carboxyl and mercapto in a molecular structure;
(2) dissolving the modified elastomer grafted by carboxyl and a compound containing any one group of hydroxyl, epoxy or amino and a photosensitive group in an organic solvent, and reacting at the temperature of 20-120 ℃ to obtain the photosensitive group grafted elastomer material.
In the present invention, the molar ratio of isolated double bonds in the mercapto-carboxyl compound and the elastomer is 0.01: 1-1: 1; the molar ratio of hydroxyl, epoxy or amino in the photosensitive group-containing compound to hydroxyl on the modified elastomer after hydroxyl grafting is 0.01: 1-1: 1.
in the present invention, in the step (1), the mercaptocarboxyl compound is any one selected from mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, 6-mercaptohexanoic acid, 7-mercaptoheptanoic acid, 8-mercaptooctanoic acid, 11-mercaptoundecanoic acid, or 16-mercaptohexadecanoic acid;
in the present invention, in the step (1), the photoinitiator is a radical photoinitiator or a cationic photoinitiator. In the invention, the free radical photoinitiator is one or a combination of more of benzoin ethers, dialkoxyacetophenone, xanthone, thioether benzophenone containing sulfide, thioxanthone, anthraquinone and benzophenone and derivatives thereof; the cationic photoinitiator is any one of diaryl iodide, triaryl sulfide, diaryl iodonium copper salt or ferrocenium salt.
In the present invention, in the steps (1) and (2), the organic solvent is any one selected from tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, or xylene.
In the invention, the carbon nano material is selected from any one or more of nanotubes, graphene, C60 or graphene oxide.
The invention also provides a preparation method of the hybrid material with the ultraviolet light induced gradient structure, which is characterized in that the elastomer material grafted by the photosensitive group and the carbon nano material are dissolved in the organic solvent according to the proportion, the mixture is uniformly dispersed, a film is formed by a casting method, and the film material, namely the hybrid material with the ultraviolet light induced gradient structure, is prepared by drying and removing the organic solvent. Wherein: the organic solvent is selected from tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene or xylene.
Further, the invention provides an application of the hybrid material with the ultraviolet light induced gradient structure in the aspect of thermal response shape transformation. The application method specifically comprises the following steps:
firstly, pre-stretching the hybrid material with an ultraviolet light induced gradient structure under the heating condition to ensure that the stretching rate is between 10 percent and the breaking elongation, then cooling to room temperature to obtain a composite material film, and then irradiating the composite material film with ultraviolet light with the wavelength of more than 300nm (preferably 365nm) to form a gradient structure in the vertical direction; or adding a template of a pattern according to the requirement, and carrying out selective design on the structure of the film in the horizontal direction to obtain a gradient structure in the horizontal direction; and heating or infrared irradiating the film after ultraviolet irradiation to realize shape conversion.
In the invention, the heating temperature is between 60 and 120 ℃.
In the invention, the gradient structure formed by the hybrid material is erased by ultraviolet irradiation (preferably 254nm) with the wavelength less than 300nm or at the temperature of 150-200 ℃, and the membrane is restored to the original shape.
Still further, the invention provides an application of the hybrid material with the ultraviolet light induced reversible gradient structure in the aspect of solvent-responsive shape transformation. The application method comprises the following steps:
firstly, irradiating the hybrid material with an ultraviolet light induced gradient structure by using ultraviolet light with the wavelength of more than 300nm to form a gradient structure in the vertical direction; a template of a pattern can be added according to the requirement, and the structure of the film is selectively designed in the horizontal direction to obtain a gradient structure in the horizontal direction; soaking the film irradiated by the ultraviolet light in a good solvent, after the film is swelled and balanced, the film curls towards the irradiation direction, then taking out the film, soaking the film in a poor solvent, and recovering the curled film to the original flat state.
Or the application method comprises the following steps:
firstly, soaking the hybrid material with the ultraviolet light induced gradient structure in a good solvent, irradiating the hybrid material with ultraviolet light with the wavelength of more than 300nm (preferably 365nm) after the hybrid material is swelled and balanced, forming the gradient structure in the vertical direction in the irradiation process, taking out the hybrid material, soaking the hybrid material in a poor solvent, and curling the film in the direction deviating from the irradiation direction.
In the present invention, the good solvent is any one of toluene, xylene, tetrahydrofuran, chloroform, dichloromethane, cyclohexane, or benzene, and the poor solvent is any one of methanol, ethanol, acetone, butanone, or water.
In the invention, the gradient structure formed by the hybrid material is erased under the irradiation of ultraviolet light with the wavelength less than 300nm (preferably 254nm) or at the temperature of 150-200 ℃, and the membrane is restored to the original shape.
Compared with the prior art, the invention has the beneficial effects that:
the method for preparing the photosensitive group grafted elastomer by grafting the photodimerization group to the molecular chain of the elastomer material is simple, the raw materials are easy to obtain, and the cost is lower. The obtained photosensitive group grafted elastomer can be compounded with a carbon nano material to prepare a membrane material with a reversible gradient structure. The membrane with the gradient structure can realize responsive shape transformation under the condition of external stimulation. Due to the reversibility of the photodimerization reaction, the structure conversion process is reversible, so that the photosensitive group grafted elastomer carbon nano material composite material has potential application in the research field of shape conversion.
Drawings
FIG. 1 is a schematic representation of the reaction procedure and molecular structure of the carboxyl-grafted SBS of example 1.
FIG. 2 is a schematic representation of the reaction process and molecular structure of the photosensitive elastomer of anthracene-grafted SBS in example 1.
FIG. 3 is nuclear magnetic spectra of carboxy-grafted SBS and anthracene-grafted SBS of example 1.
FIG. 4 is a stress-strain curve of the composite material of example 2 with different amounts of carbon nanotubes added.
FIG. 5 is a diagram showing the shape transition of the UV-induced gradient hybrid material prepared from the photosensitive group grafted elastomer material and the carbon nanomaterial in example 3 at different elongations (100,200, 300%).
FIG. 6 is the process of preparing the hybrid material with the ultraviolet light induced gradient structure by using the photosensitive group grafted elastomer material and the carbon nanomaterial in example 4, and the process of regional shape transformation, infrared responsive transformation and thermal erasure.
FIG. 7 is the process of shape transformation of the hybrid material with UV-induced gradient structure prepared from the elastomer material grafted with photosensitive groups and carbon nanomaterials under the induction of solvent in example 5.
FIG. 8 is the process of shape transformation of the hybrid material with UV-induced gradient structure prepared from the elastomer material grafted with photosensitive groups and carbon nanomaterial in example 6 under the induction of solvent.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples. The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
SBS and mercaptopropionic acid are dissolved in toluene according to different proportions, a proper amount of photoinitiator I907 is added, the proportion is 20% in the example, and after the mixture is uniformly stirred, click reaction is carried out under ultraviolet illumination. FIG. 1 is a reaction process equation.
Dissolving carboxyl grafted SBS in toluene, adding anthracene epoxy compound
Reacting for 48 hours at the temperature of 80 ℃ to obtain the anthracene grafted SBS. The graft amount of anthracene in this example was 50% of the carboxyl group. FIG. 2 is a reaction equation for anthracene-grafted SBS. FIG. 3 is nuclear magnetic spectra of carboxy-grafted SBS and anthracene-grafted SBS of example 1.
Example 2
The anthracene-grafted SBS of example 1 and carbon nanotubes (1%, 2%, 3%, 4%, 5%) with different contents were mixed in toluene, and then heated at 0 ℃ to remove the solvent to form a film. FIG. 4 is a stress-strain curve for hybrid materials of different carbon nanotube content. As the content of the carbon nano tubes is increased, the breaking strength and the modulus of the material are increased, and the breaking elongation rate is reduced. In the system, several composite materials with carbon nanotube content have better elasticity, and in order to balance elasticity and strength performance, we select a composite material with 2% carbon nanotube content as a representative to study the responsive deformation of the composite material, but the performance is not limited to the composite material with the content.
Example 3
Pre-stretching the hybrid material (the sample containing 2% of carbon nanotube prepared in example 2) with ultraviolet induced gradient structure prepared from the elastomer material grafted with the photosensitive group and the carbon nanomaterial under the condition of heating at 80 ℃ to ensure that the stretching rates are 100%, 200% and 300% respectively, and then cooling to room temperature; the light irradiation treatment is carried out for 10 minutes by 365nm wavelength ultraviolet light, and then the treatment is carried out for 20 minutes by heating at 100 ℃. The film undergoes a shape transition as shown in fig. 5.
Example 4
The ultraviolet light induced gradient structure hybrid material sample (2% carbon nanotube sample prepared in example 2) prepared by using the elastomer material grafted with the photosensitive group and the carbon nanomaterial is pre-stretched to 50% elongation at 100 ℃, heat-treated for 30 minutes, and then cooled to room temperature. The template was treated under 365nm wavelength UV light for 20 minutes followed by heating at 100 ℃ for 20 minutes (FIG. 6A) to induce the shape transition to occur. By replacing the induced shape transition process with 808nm laser irradiation without direct heating, regional control can be achieved, as shown in fig. 6B. The sample after the shape conversion was heated to 160 ℃ for 30 minutes, the pattern was erased, and the sample was restored to the original flat shape (fig. 6C).
Example 5
Firstly, the hybrid material film (the sample containing 2% of carbon nano tube prepared in the embodiment 2) of the ultraviolet light induced gradient structure prepared by the elastomer material grafted by the photosensitive group and the carbon nano material is soaked in toluene, after the swelling balance, the hybrid material film is irradiated by ultraviolet light with the wavelength of 356nm, and the gradient structure in the vertical direction of the irradiation process is formed. After taking out and soaking in ethanol, the film curled away from the direction of light irradiation, as shown in fig. 7.
Example 6
Firstly, a hybrid material film (a sample containing 2% of carbon nano tubes prepared in example 2) with an ultraviolet light induced gradient structure prepared from an elastomer material grafted with a photosensitive group and a carbon nano material is irradiated by ultraviolet light with a wavelength of 365 nm. In this process, a gradient structure in the vertical direction is formed. And soaking the film irradiated by the ultraviolet light in toluene, and after the film is swelled and balanced, curling the film towards the irradiation direction. And then taken out and soaked in ethanol solvent, and the curled film is restored to the original flat state, and the process is shown in fig. 8.
Claims (14)
1. The hybrid material with the ultraviolet light induced gradient structure is characterized in that the hybrid material is a membrane material formed by compounding an elastomer material grafted by a photosensitive group and a carbon nano material;
wherein: the photosensitive group is a group for generating photodimerization reaction, the substrate of the elastomer material is an elastomer containing isolated double bonds, and the mass ratio of the elastomer material grafted by the photosensitive group to the carbon nano material is 1:0.001-1: 0.2;
the photosensitive group is selected from any one or more of coumarin group, anthracene group, chalcone group or cinnamate group;
the matrix of the elastomer material is selected from any one of butadiene rubber, SBS, SIS, SIBS, nitrile rubber, styrene butadiene rubber, natural rubber or EPDM;
the photosensitive group grafted elastomer is prepared by the following steps: (1) dissolving an elastomer containing isolated double bonds and a mercapto carboxyl compound in an organic solvent, uniformly stirring, adding a photoinitiator, and carrying out mercapto-alkene click reaction under the condition of ultraviolet illumination to obtain a modified elastomer after carboxyl grafting; wherein: the mercapto carboxyl compound is a compound which simultaneously contains carboxyl and mercapto in a molecular structure; (2) dissolving the modified elastomer grafted by carboxyl and a compound containing any one group of hydroxyl, epoxy or amino and a photosensitive group in an organic solvent, and reacting at the temperature of 20-120 ℃ to obtain the photosensitive group grafted elastomer material.
2. The hybrid material with gradient structure induced by ultraviolet light as claimed in claim 1, wherein the molar ratio of isolated double bonds in the mercapto carboxyl compound and the elastomer is 0.01: 1-1: 1; the molar ratio of hydroxyl, epoxy or amino in the photosensitive group-containing compound to hydroxyl on the modified elastomer after hydroxyl grafting is 0.01: 1-1: 1.
3. the hybrid material with an ultraviolet light induced gradient structure according to claim 2, wherein in the step (1), the mercapto carboxyl compound is selected from any one of thioglycolic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, 6-mercaptohexanoic acid, 7-mercaptoheptanoic acid, 8-mercaptooctanoic acid, 11-mercaptoundecanoic acid, or 16-mercaptohexadecanoic acid.
4. The hybrid material with the ultraviolet light induced gradient structure as claimed in claim 1, wherein the carbon nanomaterial is selected from any one or more of nanotube, graphene, C60 or graphene oxide.
5. The method for preparing the hybrid material with the ultraviolet light-induced gradient structure according to claim 1, wherein the film material, namely the hybrid material with the ultraviolet light-induced gradient structure, is prepared by dissolving an elastomer material grafted with a photosensitive group and a carbon nano material in an organic solvent according to a proportion, uniformly dispersing, forming a film by a casting method, and drying to remove the organic solvent.
6. Use of the hybrid material of the ultraviolet light induced gradient structure of claim 1 for shape transformation of thermal response or infrared light response.
7. The application according to claim 6, wherein the application method is as follows: firstly, pre-stretching the hybrid material with an ultraviolet light induced gradient structure under the heating condition to ensure that the stretching rate is between 10 percent and the elongation at break, then cooling to room temperature to obtain a composite material film, and then irradiating the composite material film by using ultraviolet light with the wavelength of more than 300nm to form a gradient structure in the vertical direction; or adding a template of a pattern according to the requirement, and carrying out selective design on the structure of the film in the horizontal direction to obtain a gradient structure in the horizontal direction; the film after the ultraviolet irradiation is subjected to heating or infrared irradiation treatment to realize shape conversion.
8. Use according to claim 7, wherein the temperature of heating is between 60 and 120 ℃.
9. The use of claim 8, wherein the membrane is restored to its original shape by irradiating the membrane with UV light of less than 300nm or erasing the gradient structure formed by the hybrid material at a temperature of 150-200 ℃.
10. Use of a hybrid material of the ultraviolet light-induced reversible gradient structure according to claim 1 for solvent-responsive shape transformation.
11. Use according to claim 10, characterised in that it is applied by the following steps:
firstly, irradiating the hybrid material with an ultraviolet light induced gradient structure by using ultraviolet light with the wavelength of more than 300nm to form a gradient structure in the vertical direction; a template of a pattern can be added according to the requirement, and the structure of the film is selectively designed in the horizontal direction to obtain a gradient structure in the horizontal direction; soaking the film irradiated by the ultraviolet light in a good solvent, after the film is swelled and balanced, the film curls towards the irradiation direction, then taking out the film, soaking the film in a poor solvent, and recovering the curled film to the original flat state.
12. Use according to claim 10, characterised in that it is applied by the following steps: firstly, soaking the hybrid material with the ultraviolet light induced gradient structure in a good solvent, irradiating by ultraviolet light with the wavelength of more than 300nm after the hybrid material is balanced in swelling, forming a gradient structure in the vertical direction in the irradiation process, then taking out, soaking in a poor solvent, and curling the film in the direction deviating from the irradiation direction.
13. Use according to claim 11 or 12, wherein the good solvent is any one of toluene, xylene, tetrahydrofuran, chloroform, dichloromethane, cyclohexane or benzene, and the poor solvent is any one of methanol, ethanol, acetone, butanone or water.
14. The use of claim 11 or 12, wherein the gradient structure formed by the hybrid material is erased under the irradiation of ultraviolet light with a wavelength of less than 300nm or at a temperature of 150-200 ℃, and the membrane returns to the original shape.
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| CN111205382B (en) * | 2020-02-12 | 2021-05-11 | 大连理工大学 | Photoresponse ethylene propylene diene monomer and preparation method thereof |
| CN111607046B (en) * | 2020-06-16 | 2021-03-26 | 浙江大学 | Concentration/modulus bidirectional gradient hydrogel for high-throughput screening of biological materials and preparation method thereof |
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| CN105602181A (en) * | 2015-12-28 | 2016-05-25 | 上海交通大学 | Carbon nanotube modified thermoplastic elastomer composite material with solvent resistance and preparing method thereof |
| CN106947040A (en) * | 2017-03-10 | 2017-07-14 | 上海交通大学 | Ultraviolet-sensitive elastomeric material, synthetic method and its application in terms of two-dimensional relief pattern and three-dimensional complex shapes is built |
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| CN105602181A (en) * | 2015-12-28 | 2016-05-25 | 上海交通大学 | Carbon nanotube modified thermoplastic elastomer composite material with solvent resistance and preparing method thereof |
| CN106947040A (en) * | 2017-03-10 | 2017-07-14 | 上海交通大学 | Ultraviolet-sensitive elastomeric material, synthetic method and its application in terms of two-dimensional relief pattern and three-dimensional complex shapes is built |
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