Construction method of three-dimensional surface fold structure and three-dimensional structure material

Abstract

The invention relates to the technical field of high polymer materials, in particular to a construction method of a three-dimensional surface fold structure and a three-dimensional structure material. According to the construction method of the three-dimensional surface wrinkle structure, the top-to-bottom 3D printing technology and the bottom-to-top self-wrinkle structuring technology are combined, gradient crosslinking is induced through photo-crosslinking curing in the 3D printing process, the self-wrinkle structure is formed on the surface by means of material stress instability, and the self-wrinkle structuring effect is achieved. The synchronous construction of a macrostructure and a surface microcosmic pattern is realized, and the expansion of a surface wrinkle structure from a two-dimensional plane to a three-dimensional structure is realized. The three-dimensional structure material with the near-infrared response characteristic and the wrinkle structure on the surface can be prepared through the construction method, in-situ dynamic regulation and control of the wrinkle structure on the surface of the three-dimensional structure material are achieved, and the three-dimensional structure material has wide application prospects in the fields of intelligent devices, adjustable structure materials and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and particularly relates to a method for constructing a three-dimensional surface wrinkle structure and a three-dimensional structure material. BACKGROUND

[0002] Wrinkle structures can endow material surfaces with rich functional properties, and have wide applications in the fields of bionic materials, flexible devices, optical regulation, wetting regulation, and mechanical property enhancement. Traditional wrinkle structure construction mainly relies on material surface mechanical instability strategies, such as thermal shrinkage, mechanical pre-stretch release, and solvent swelling. These strategies usually rely on two-dimensional planar substrates, and wrinkle structures are formed by stress release on the surface of the substrates. However, with the development of material science and micro-nano manufacturing technology, two-dimensional surface wrinkle structures have been difficult to meet the requirements of complex structure devices in terms of integration and functionality.

[0003] Expanding wrinkle structures from two-dimensional planes to three-dimensional structures can not only improve the spatial structure freedom of materials, but also endow them with more rich physical and chemical response behaviors, and show a broader application prospect in the fields of mechanical regulation, biomedical engineering, microelectronic devices, and micro-nano photonics. Current mainstream surface wrinkle structure manufacturing technologies such as photolithography and nano-imprinting are based on planar processes, and are difficult to be directly used for the construction of three-dimensional surface wrinkle structures. Therefore, developing a construction method suitable for three-dimensional surface wrinkle structures has important scientific significance and application value.

[0004] In recent years, various emerging technologies have been tried for the construction of three-dimensional surface wrinkle structures, such as multilayer stacking, laser direct writing, 3D printing, etc., but there are still many challenges for the construction of three-dimensional surface wrinkle structures. For example, the Chinese patent application with publication number CN114750470 A discloses a composite film with isolated three-dimensional surface wrinkle microstructure and a preparation method thereof. By designing the structure of the composite film, a substrate is used as a support layer, a polymer substrate and a metal film with isolated three-dimensional wrinkle structure on the surface are sequentially arranged on one side of the substrate, and a composite film with isolated three-dimensional wrinkle structure on the surface is finally obtained through a specific preparation method. However, this patent application is only suitable for the construction of surface wrinkle structure of specific two-dimensional planar substrate (metal film), and is still limited to two-dimensional planar substrate, and it is difficult to realize the selective preparation of three-dimensional surface wrinkle structure. The Chinese patent application with publication number CN114683533 A discloses a 3D printing method for preparing arbitrary nano-wrinkle structure, product and application. The laser for 3D printing is irradiated in the precursor solution to realize the surface wrinkling of the voxel unit. By continuously changing the laser irradiation area, a plurality of connected wrinkled voxel units are generated, and after development and drying, a nano-wrinkle structure from point to surface and from surface to body is obtained. Although this patent application has made progress in the preparation of three-dimensional surface wrinkle structure, the preparation process needs to go through a complex development step, the operation is complex, and it is difficult to realize the dynamic regulation of micro-nano scale wrinkle structure.

[0005] Therefore, it is an urgent problem to explore a new construction strategy for three-dimensional surface wrinkle structure with simple process. SUMMARY

[0006] In order to solve the problems raised in the background art, the purpose of the present application is to provide a construction method of three-dimensional surface wrinkle structure.

[0007] The application provides a three-dimensional surface wrinkle structure construction method, which combines a "top-down" 3D printing technology (photocuring 3D printing) and a "bottom-up" self-wrinkle structuring technology, induces gradient crosslinking through photocuring and solidification in a 3D printing process, forms a self-wrinkle structure on a surface by utilizing material stress instability, realizes synchronous construction of a macrostructure and a surface micro-pattern, realizes expansion of a surface wrinkle structure from a two-dimensional plane to a three-dimensional structure, and is a universal strategy for constructing a wrinkle structure on a three-dimensional macrostructure surface. The construction process is simple, an integrated printing-wrinkle structure synchronous construction mode is adopted, a multi-step processing procedure required in traditional three-dimensional surface micro-patterning is simplified, construction efficiency is improved, the constructed wrinkle structure is stable, and the size of the wrinkle structure is micro-nanometer, so that the three-dimensional surface wrinkle structure construction method has potential application values in the fields of flexible electronics, biological interface engineering and intelligent camouflage. In addition, the three-dimensional surface wrinkle structure construction method can also be used to prepare a three-dimensional structure material with a near-infrared response characteristic and a surface with a wrinkle structure, realize in-situ dynamic regulation of the surface wrinkle structure, and be expanded to be applied to intelligent response type surface wrinkle structure construction, so that the three-dimensional surface wrinkle structure construction method has broad application prospects in the fields of intelligent devices and adjustable structure materials.

[0008] The first aspect of the application provides a three-dimensional surface wrinkle structure construction method, which comprises the following steps:

[0009] (1) dissolving a fluorine-containing macromolecular photoinitiator, a multifunctional acrylate crosslinking agent and an acrylate oligomer in an organic solvent to prepare a 3D printing resin solution, or mixing the fluorine-containing macromolecular photoinitiator, the multifunctional acrylate crosslinking agent, the acrylate oligomer and a graphene solution to prepare the 3D printing resin solution;

[0010] (2) using photocuring 3D printing to make the 3D printing resin solution in the printing process occur crosslinking and solidification under light and be deposited on a substrate to obtain a single-layer deposited material with a self-wrinkle structure on the surface;

[0011] (3) repeating step (2) to finally stack a three-dimensional structure material through layer-by-layer deposition;

[0012] (4) performing heat treatment and photocuring solidification treatment on the three-dimensional structure material to obtain a three-dimensional structure material with a wrinkle structure on the surface.

[0013] The three-dimensional surface wrinkle structure construction method described above, the structure of the fluorine-containing macromolecular photoinitiator is shown in formula (1) or formula (2):

[0014] Formula (1) Formula (2)

[0015] In formula (1) or formula (2), 0 < x ≤ 100, 0 < y ≤ 100, and 0 < z ≤ 100.

[0016] The method for constructing the three-dimensional surface wrinkle structure as described above, in step (1), the mass fraction of the fluorine-containing macromolecular photoinitiator in the 3D printing resin solution is 4-15 wt%.

[0017] And / or, in step (1), the mass ratio of the fluorine-containing macromolecular photoinitiator, the multifunctional acrylate crosslinking agent, and the acrylate oligomer is (2-10):(5-50):(5-50).

[0018] The method for constructing the three-dimensional surface wrinkle structure as described above, in step (1), the graphene solution is prepared by dissolving graphene in an organic solvent, and the mass fraction of the graphene solution is 0.2 wt%-2 wt%.

[0019] The method for constructing the three-dimensional surface wrinkle structure as described above, in step (1), the solid content mass percentage of the 3D printing resin solution is 20%-80%.

[0020] The method for constructing the three-dimensional surface wrinkle structure as described above, in step (2), the process parameters of the photocuring 3D printing include:

[0021] The extrusion speed of the peristaltic pump is controlled to be 1 mL / hr-10 mL / hr;

[0022] The printing speed is controlled to be 5 mm / s-30 mm / s;

[0023] The inner diameter of the printing nozzle is controlled to be 0.4 mm-0.8 mm;

[0024] The printing thickness of each layer is controlled to be 10 μm-50 μm;

[0025] The light irradiation conditions include: the wavelength of the ultraviolet light is 315 nm-400 nm, and the intensity is 10 mW / cm 2 -100 mW / cm 2 .

[0026] The method for constructing the three-dimensional surface wrinkle structure as described above, in step (4), the light crosslinking curing treatment includes: irradiation under ultraviolet light with a wavelength of 315 nm-400 nm and an intensity of 10 mW / cm 2 -100 mW / cm 2 for 5 min-20 min.

[0027] The method for constructing the three-dimensional surface wrinkle structure as described above, in step (4), the temperature of the heat treatment is 35℃-50℃, and the time is 30 min-90 min.

[0028] The method for constructing a three-dimensional surface wrinkle structure, wherein the multifunctional acrylate crosslinking agent is at least one of 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, glycerol trihydroxypropyl ether triacrylate, and pentaerythritol tetraacrylate.

[0029] The acrylate oligomer is at least one of polyether acrylate, aliphatic polyurethane triacrylate, and polyester acrylate.

[0030] The second aspect of the present application provides a three-dimensional structure material with a surface wrinkle structure, which is prepared by the method for constructing a three-dimensional surface wrinkle structure.

[0031] The method for constructing a three-dimensional surface wrinkle structure has at least the following effects:

[0032] The method for constructing a three-dimensional surface wrinkle structure constructs a macro three-dimensional structure material by using a “top-down” 3D printing technology (light curing 3D printing), and simultaneously generates a micro-nano scale wrinkle structure on the surface of the three-dimensional structure material by using a “bottom-up” self-wrinkling technology, so as to realize the synchronous construction of a macro structure and a surface micro pattern, and realize the expansion of the surface wrinkle structure from a two-dimensional plane to a three-dimensional structure. The method is a universal strategy for constructing a wrinkle structure on the surface of a three-dimensional macro structure. The method uses an integrated printing-wrinkle structure synchronous construction mode, and the construction process is simple, so that the multi-step processing procedure required by a traditional three-dimensional surface micro patterning is simplified, the construction efficiency is improved, and the wrinkle structure constructed is stable and has a micro-nano scale, so that the method has potential application value in the fields of flexible electronics, biological interface engineering, and intelligent camouflage. The method ensures the stability of the wrinkle structure in morphology and mechanical properties by integrated design of a three-dimensional structure material formula, so that the service life of the wrinkle structure is significantly prolonged. The method can finely control the wavelength and amplitude of the three-dimensional surface wrinkle structure by controlling parameters such as light intensity and extrusion speed, so as to meet the requirements of different application scenarios for structure size and functional response. Researches show that the method can prepare a three-dimensional structure material with a surface wrinkle structure having near-infrared response characteristics by introducing a functional unit (graphene in the embodiment of the present application) that responds to external stimuli such as light and heat into a three-dimensional structure material formula, so as to realize in-situ dynamic regulation of the surface wrinkle structure, and can be applied to the construction of an intelligent response type surface wrinkle structure, and has broad application prospects in the fields of intelligent devices and adjustable structure materials.

[0033] The present invention provides a three-dimensional structural material with a wrinkled surface, which is prepared by the aforementioned method for constructing a three-dimensional surface wrinkled structure. Compared with the problems of unadjustable surface wrinkles and difficulty in dynamic control in the preparation of traditional three-dimensional structural materials, the present invention introduces a collaborative construction mechanism of printing configuration and surface wrinkles, simultaneously completing the three-dimensional structural forming and the generation of surface micro-wrinkles in a one-step printing process, eliminating the need for additional development, washing, and drying processes, thus significantly reducing processing complexity and environmental burden. Furthermore, by introducing functional units (graphene in this embodiment) that respond to external stimuli such as light / heat into the raw material formulation of the three-dimensional structural material, the present invention endows the surface wrinkles of the three-dimensional structural material with in-situ reversible dynamic control capabilities, realizing dynamic control of the surface wrinkles of the three-dimensional structural material. This effectively solves the problem of the difficulty in achieving dynamic control of the surface of traditional three-dimensional structural materials, providing a new approach for constructing integrated intelligent structures with sensing, response, and reconfigurability functions. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This is a synthetic route diagram of the fluorine-containing macromolecular photoinitiator I in Example 1 of the present invention;

[0036] Figure 2 The above is the 1H NMR spectrum of the random copolymer containing dimethylamino in Example 1 of this invention;

[0037] Figure 3 This is the 1H NMR spectrum of the fluorine-containing macromolecular photoinitiator I in Example 1 of the present invention;

[0038] Figure 4 This is a synthetic route diagram of the fluorine-containing macromolecular photoinitiator II in Example 2 of the present invention;

[0039] Figure 5 This is the 1H NMR spectrum of the fluorine-containing macromolecular photoinitiator II in Example 2 of the present invention;

[0040] Figure 6 The images shown are a preset path diagram for photopolymer 3D printing in Embodiment 3 of the present invention, and a physical image and surface morphology diagram of a three-dimensional structural material with a wrinkled surface. Figure 6 'a' represents the preset path diagram for photopolymer 3D printing. Figure 6b is a physical map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface, Figure 6 c is a surface topography map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface;

[0041] Figure 7 is a preset path map of light-cured 3D printing and a physical map and a surface topography map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface in Example 4 of the present application, wherein Figure 7 a is a preset path map of light-cured 3D printing, Figure 7 b is a physical map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface, Figure 7 c is a three-dimensional surface topography map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface; Figure 7 d is a two-dimensional surface topography map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface;

[0042] Figure 8 is a surface wrinkled structure in situ dynamic regulation map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface in Example 5 of the present application; wherein, Figure 8 a is a surface wrinkled structure map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface, Figure 8 b is an enlarged view of the surface wrinkled structure of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface, Figure 8 c is a surface wrinkled structure map of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface after irradiation with 808 nm near-infrared light, Figure 8 d is an enlarged view of the surface wrinkled structure of the three-dimensional stereoscopic structure material with a wrinkled structure on the surface after irradiation with 808 nm near-infrared light;

[0043] Figure 9 is a surface topography map of the three-dimensional stereoscopic structure material in Comparative Example 1 of the present application;

[0044] Figure 10 is a surface topography map of the three-dimensional stereoscopic structure material in Comparative Example 2 of the present application;

[0045] Figure 11 is a physical map of the three-dimensional stereoscopic structure material in Comparative Example 3 of the present application;

[0046] Figure 12 is a physical map of the three-dimensional stereoscopic structure material in Comparative Example 4 of the present application;

[0047] Figure 13 is a surface topography map of the three-dimensional stereoscopic structure material in Comparative Example 5 of the present application;

[0048] Figure 14 is a surface topography map of the three-dimensional stereoscopic structure material in Comparative Example 6 of the present application;

[0049] Figure 15 Surface topography of the three-dimensional stereoscopic structure material in the present application comparative example 7;

[0050] Figure 16 Surface topography of the three-dimensional stereoscopic structure material in the present application comparative example 8;

[0051] Figure 17 Surface topography of the three-dimensional stereoscopic structure material in the present application comparative example 9;

[0052] Figure 18 Surface topography of the three-dimensional stereoscopic structure material in the present application comparative example 10;

[0053] Figure 19 Surface wrinkle structure in situ dynamic regulation diagram of the three-dimensional stereoscopic structure material with surface wrinkle structure in the present application comparative example 11, wherein, Figure 19 a is the surface wrinkle structure diagram of the three-dimensional stereoscopic structure material with surface wrinkle structure, Figure 19 b is the surface wrinkle structure diagram of the three-dimensional stereoscopic structure material with surface wrinkle structure after 808 nm near-infrared light irradiation;

[0054] Figure 20 Surface wrinkle structure topography of the three-dimensional stereoscopic structure material with surface wrinkle structure in the present application comparative example 12. DETAILED DESCRIPTION

[0055] In order to make the objects, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. If the specific technology or condition is not mentioned in the embodiments, it is carried out according to the technology or condition described in the literature in the art or according to the product instruction. If the reagent or instrument used is not mentioned by the manufacturer, it is a conventional product that can be obtained by market purchase.

[0056] It should be noted that the description of "first", "second", "third" and the like in the present application is used to distinguish similar objects, and is not used to describe a specific order or sequence, and therefore should not be understood as a limitation on the present application.

[0057] It will be understood by those within the art that, in this application, any numerical range recited is intended to include all sub-ranges of the same numbers. In any statement of a range, any numerical upper limit, whether stated or not, can be replaced with another numerical lower limit, and, vice versa. These are not to be taken as limiting the preferred embodiments described herein.

[0058] Unless defined otherwise, technical / scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this application belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the preferred methods and materials are described. All documents mentioned herein are incorporated by reference to disclose and describe in further detail the methods and / or materials associated with the documents. In the case of conflict between the present specification and any document incorporated herein by reference, the present specification will control.

[0059] A first aspect of the present application provides a method for constructing a three-dimensional surface wrinkle structure, comprising the following steps:

[0060] (1) dissolving a fluorine-containing macromolecular photoinitiator, a multi-functionality acrylate crosslinking agent and an acrylate oligomer in an organic solvent to prepare a 3D printing resin solution, or mixing the fluorine-containing macromolecular photoinitiator, the multi-functionality acrylate crosslinking agent, the acrylate oligomer and a graphene solution to prepare a 3D printing resin solution;

[0061] (2) using light-curing 3D printing, the 3D printing resin solution in the printing process is cross-linked and cured under light conditions and deposited on a substrate to obtain a single-layer deposited material with a self-wrinkled structure on the surface;

[0062] (3) repeating step (2) to finally accumulate a three-dimensional structure material by layer-by-layer deposition;

[0063] (4) performing heat treatment and light cross-linking curing treatment on the three-dimensional structure material to obtain a three-dimensional structure material with a wrinkled structure on the surface.

[0064] In step (1), the 3D printing resin solution can be composed of a fluorine-containing macromolecular photoinitiator, a multi-functionality acrylate crosslinking agent, an acrylate oligomer and an organic solvent, or can be composed of a fluorine-containing macromolecular photoinitiator, a multi-functionality acrylate crosslinking agent, an acrylate oligomer and a graphene solution.

[0065] In step (2), the light-cured 3D printing is adopted, so that the 3D printing resin solution is cross-linked and cured under light irradiation during the printing process and is deposited on the substrate; during the cross-linking and curing process, the fluorine-containing macromolecular photoinitiator can be enriched on the surface layer of the 3D printing resin solution due to the low surface energy characteristics of the fluorine-containing macromolecular photoinitiator, so that the surface layer of the 3D printing resin solution is gradiently cross-linked, which causes the mismatch of thermal expansion and shrinkage rates between the surface layer and the inner layer of the 3D printing resin solution; during the volatilization of the organic solvent and the cooling of the material, the shrinkage degree of the inner layer is higher than that of the surface layer, so that a self-pleated structure is formed on the surface layer, and a single-layer deposited material with a self-pleated structure on the surface is obtained.

[0066] In step (4), the heat treatment is to volatilize the residual organic solvent in the three-dimensional structure material; and the light cross-linking and curing treatment is to further cross-link and cure the whole three-dimensional structure material, so as to form a stable pleated structure, and finally obtain a three-dimensional structure material with a pleated structure on the surface.

[0067] In the present application, the organic solvent in step (1) is a conventional type. For example, the above-mentioned organic solvent is at least one of chloroform, 1,4-dioxane, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetrahydrofuran, acetone, trifluorotoluene.

[0068] The present application does not particularly limit the specific shape of the above-mentioned three-dimensional structure material, which can be selected according to actual needs, for example, a three-dimensional structure material with different shapes can be prepared by changing the printing path.

[0069] The present application does not particularly limit the specific thickness of the above-mentioned three-dimensional structure material, which can be selected according to actual needs.

[0070] In the present application, the above-mentioned substrate is a conventional substrate, for example, the above-mentioned substrate can be plastic (such as polyethylene terephthalate (PET), polymethyl methacrylate (PMMA)), metal (such as copper, iron, aluminum), glass, etc.

[0071] The present application does not limit the shape, size and thickness of the substrate, which can be selected according to actual needs.

[0072] The application provides a three-dimensional surface wrinkle structure construction method, which constructs a macro three-dimensional structure material through a 3D printing technology from top to bottom (the application adopts a light curing 3D printing technology), and synchronously generates a micro-nano scale wrinkle structure on the surface of the three-dimensional structure material through a self-wrinkling structure technology from bottom to top, so that the macro structure and the surface micro pattern are constructed synchronously, the surface wrinkle structure is expanded from a two-dimensional plane to a three-dimensional structure, and the application is a universal strategy for constructing a wrinkle structure on the surface of a three-dimensional macro structure. The application adopts an integrated printing-wrinkle structure synchronous construction mode, the construction process is simple, the multi-step processing procedure required by traditional three-dimensional surface micro patterning is simplified, the construction efficiency is improved, and the wrinkle structure constructed has a micro-nano scale, and has potential application value in the fields of flexible electronics, biological interface engineering and intelligent camouflage. The application ensures the stability of the wrinkle structure in morphology and mechanical properties through integrated design of a three-dimensional structure material raw material formula, and significantly prolongs the service life of the wrinkle structure. The application can finely control the wavelength and amplitude of the three-dimensional surface wrinkle structure by controlling parameters such as light intensity and extrusion speed, so as to meet the requirements of different application scenarios on structure size and functional response.

[0073] When step (1) is mixing the fluorine-containing macromolecular photoinitiator, the multifunctional acrylate crosslinking agent, the acrylate oligomer and the graphene solution to prepare the 3D printing resin solution, the three-dimensional structure material with the surface having the wrinkle structure finally prepared has near-infrared response characteristics, in-situ dynamic regulation of the three-dimensional surface wrinkle structure is realized, the application can be expanded to construction of an intelligent response type surface wrinkle structure, and the application has broad application prospects in the fields of intelligent devices and adjustable structure materials.

[0074] In a specific embodiment, the structure of the fluorine-containing macromolecular photoinitiator is shown in formula (1) or formula (2): Formula (1) Formula (2)

[0075] In formula (1) or formula (2), 0 < x ≤ 100, 0 < y ≤ 100, and 0 < z ≤ 100.

[0076] In the present application, the fluorine-containing macromolecular photoinitiator has a fluorine-containing functional monomer, and the inherent ultra-low surface energy characteristics can form a surface self-wrinkled structure in the process of gradient self-assembly layer formation of the 3D printing resin solution in the photocrosslinking curing process. Compared with the traditional small molecule photoinitiator, the fluorine-containing macromolecular photoinitiator of the present application has lower migration and higher structural stability, avoids the precipitation or degradation problem that may be caused by the small molecule photoinitiator after photocrosslinking curing, and improves the durability of the formed wrinkle structure; at the same time, the fluorine-containing macromolecular photoinitiator has better dispersibility and controllable reaction rate, so that more accurate photocrosslinking curing control can be realized in the printing process, which is helpful to build a stable wrinkle structure.

[0077] The fluorine-containing macromolecular photoinitiator with a structure as shown in formula (1) can be prepared by a preparation method comprising the following processes:

[0078] Dimethylaminoethyl methacrylate (DMAEMA), perfluorooctyl ethyl acrylate and a first catalyst are dissolved in a first solvent, and stirred and reacted at 70-90 DEG C for 12-18 hours, and then treated to obtain a random copolymer containing dimethylamino; the random copolymer containing dimethylamino and 4-(bromomethyl) benzophenone are dissolved in a second solvent, and stirred and reacted at 60-80 DEG C for 12-24 hours to obtain the fluorine-containing macromolecular photoinitiator with a structure as shown in formula (1).

[0079] The molar ratio of the above-mentioned dimethylaminoethyl methacrylate, perfluorooctyl ethyl acrylate and the first catalyst is (30-50):10:(1-2); the molar ratio of the above-mentioned random copolymer containing dimethylamino and 4-(bromomethyl) benzophenone is (30-60):(20-40).

[0080] The above-mentioned first solvent is selected from at least one of 1,4-dioxane, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetrahydrofuran, acetone and trifluorotoluene.

[0081] The above-mentioned second solvent is selected from at least one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetrahydrofuran, acetone and toluene.

[0082] The above-mentioned first catalyst comprises azobisisobutyronitrile (AIBN).

[0083] The fluorine-containing macromolecular photoinitiator with a structure as shown in formula (2) can be prepared by a preparation method comprising the following processes:

[0084] The dimethylaminoethyl methacrylate (DMAEMA), 4-acryloyl hydroxybenzoic acid phenone, perfluorooctyl ethyl acrylate and the second catalyst are dissolved in the third solvent, and stirred at 70-90°C for 12-18h, and the fluorine-containing macromolecular photoinitiator with structure shown in formula (2) is obtained after post-treatment.

[0085] The molar ratio of the dimethylaminoethyl methacrylate, 4-acryloyl hydroxybenzoic acid phenone, perfluorooctyl ethyl acrylate and the second catalyst is (20-40):(40-70):(10-20):(1-2).

[0086] The third solvent is at least one selected from 1, 4-dioxane, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, tetrahydrofuran, acetone, trifluorotoluene.

[0087] The second catalyst includes azobis isobutyronitrile (AIBN).

[0088] In a specific embodiment, the mass fraction of the fluorine-containing macromolecular photoinitiator in the 3D printing resin solution is 4-15wt%.

[0089] When the mass fraction of the fluorine-containing macromolecular photoinitiator in the 3D printing resin solution is in the above range, a three-dimensional structure material with a surface having a disordered micron-scale wrinkle structure can be prepared. If the content of the fluorine-containing macromolecular photoinitiator is too low (such as the mass fraction of the fluorine-containing macromolecular photoinitiator in the 3D printing resin solution is 2wt%), the curing of the three-dimensional structure material will not be complete, resulting in the material surface being unable to form a wrinkle structure; if the content of the fluorine-containing macromolecular photoinitiator is too high (such as the mass fraction of the fluorine-containing macromolecular photoinitiator in the 3D printing resin solution is 20wt%), the three-dimensional structure material will be severely phase separated, and a disordered micron-scale wrinkle structure cannot be constructed on the material surface.

[0090] In a specific embodiment, in step (1), the mass ratio of the fluorine-containing macromolecular photoinitiator, the multifunctional acrylate crosslinking agent and the acrylate oligomer is (2-10):(5-50):(5-50).

[0091] When the mass ratio of the fluorine-containing macromolecular photoinitiator, the multi-functional acrylate crosslinking agent and the acrylate oligomer in step (1) is within the above range, the fluorine-containing macromolecular photoinitiator rapidly absorbs ultraviolet light and forms active radicals under light irradiation, preferentially initiates the double bond of the acrylate oligomer to open and form chain growth; the multi-functional acrylate crosslinking agent rapidly connects the linear polymer chains into a network through multiple reaction sites, improves the crosslinking density of the system, accelerates the curing speed of the material, and forms a gradient system while the material is photocured and crosslinked, thereby forming a wrinkle structure on the surface of the material.

[0092] In a specific embodiment, the graphene solution in step (1) is prepared by dissolving graphene in an organic solvent, and the mass fraction of the graphene solution is 0.2wt%-2wt%.

[0093] The specific type of the organic solvent for preparing the graphene solution is not particularly limited in the present application. In some embodiments, the organic solvent in the graphene solution is at least one of chloroform, 1,4-dioxane, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetrahydrofuran, acetone, and trifluorotoluene.

[0094] Graphene has good photo-thermal conversion effect. The present application mixes graphene with a fluorine-containing macromolecular photoinitiator, a multi-functional acrylate crosslinking agent and an acrylate oligomer to prepare a three-dimensional material with a wrinkle structure on the surface, which has near-infrared response characteristics. As shown in Figure 8 As shown in the figure, under 808 nm near-infrared light irradiation, the system temperature of the three-dimensional material with a wrinkle structure on the surface rapidly increases and expands, and the surface wrinkle structure is erased. After the 808 nm near-infrared light irradiation is removed, the system temperature decreases and the volume shrinks, resulting in the recovery of the surface wrinkle structure. This indicates that the present application realizes in-situ dynamic regulation of the surface wrinkle structure of the three-dimensional material.

[0095] When the mass fraction of the graphene solution is in the above range, the three-dimensional material with a surface having a wrinkle structure and a near-infrared response characteristic can be prepared. If the mass fraction of the graphene solution is too low (for example, the mass fraction of the graphene solution is 0.05 wt%), the surface wrinkle structure of the prepared three-dimensional material with a surface having a wrinkle structure cannot be completely erased under the irradiation of 808 nm near-infrared light, and the in-situ dynamic regulation of the surface wrinkle structure cannot be achieved. If the mass fraction of the graphene solution is too high (for example, the mass fraction of the graphene solution is 4 wt%), not only the uniformity of the 3D printing resin solution will be affected, but also the mechanical properties of the material as a whole will be affected. The uneven mixing of the 3D printing resin solution will directly affect the generation effect of the surface wrinkle structure, and the wrinkle structure on the surface of the prepared three-dimensional material is uneven.

[0096] Exemplarily, the mass fraction of the graphene solution can be any one or a range consisting of any two of 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%.

[0097] In one specific embodiment, in step (1), the solid content mass percentage of the 3D printing resin solution is 20%-80%.

[0098] When the solid content mass percentage of the 3D printing resin solution is in the above range, the printing precision and the solidification forming of the three-dimensional structure can be better controlled. If the solid content mass percentage of the 3D printing resin solution is too low (for example, the solid content mass percentage of the 3D printing resin solution is 10%), it cannot be quickly solidified due to its high fluidity during extrusion, and it is difficult to build a three-dimensional structure. If the solid content mass percentage of the 3D printing resin solution is too high (for example, the solid content mass percentage of the 3D printing resin solution is 100%), the resin fluidity is too low and it cannot be well extruded, resulting in low precision in the layer-by-layer stacking printing process, and the three-dimensional material with uneven concave-convex and uneven thickness is prepared.

[0099] Exemplarily, in step (1), the solid content mass percentage of the 3D printing resin solution can be any one or a range consisting of any two of 20%, 30%, 40%, 50%, 60%, 70%, 80%.

[0100] In a specific embodiment, in step (2), the process parameters of the above light-cured 3D printing include: controlling the extrusion speed of the peristaltic pump to be 1 mL / hr-10 mL / hr, for example, 1 mL / hr, 2 mL / hr, 3 mL / hr, 4 mL / hr, 5 mL / hr, 6 mL / hr, 7 mL / hr, 8 mL / hr, 9 mL / hr, 10 mL / hr, etc.; controlling the printing speed to be 5 mm / s-30 mm / s, for example, 5 mm / s, 10 mm / s, 15 mm / s, 20 mm / s, 25 mm / s, 30 mm / s, etc.; controlling the inner diameter of the printing nozzle to be 0.4 mm-0.8 mm, for example, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, etc.; controlling the printing thickness of each layer to be 10 μm-50 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, etc.; and the light irradiation conditions include: the wavelength of the ultraviolet light is 315 nm-400 nm, and the intensity is 10 mW / cm 2 -100 mW / cm 2 .

[0101] In the present application, the extrusion speed of the peristaltic pump is controlled within the above range, so that a three-dimensional structure material with a uniform wrinkle structure on the surface can be obtained. Too fast or too slow extrusion speed will directly affect the printing quality, structural integrity and mechanical properties. If the extrusion speed is too fast (e.g., the extrusion speed of the peristaltic pump is 15 mL / hr), too much 3D printing resin solution is extruded, which leads to material accumulation and uneven solidification. If the extrusion speed is too slow (e.g., the extrusion speed of the peristaltic pump is 0.5 mL / hr), the 3D printing resin solution cannot continuously cover the preset path, resulting in surface defects. Moreover, since the extrusion process is accompanied by light irradiation, the printing nozzle may be blocked.

[0102] In the present application, the inner diameter of the printing nozzle is controlled within the above range, which has a higher printing efficiency. If the inner diameter of the printing nozzle is too small (e.g., the inner diameter of the printing nozzle is 0.2 mm), the printing speed is slow, the interlayer bonding force may be insufficient, the surface wrinkle structure is oriented to a certain extent, and there is a risk of blocking the printing nozzle. If the inner diameter of the printing nozzle is too small (e.g., the inner diameter of the printing nozzle is 1 mm), the fineness of the surface wrinkle structure will be sacrificed, resulting in loss of details and excessive extrusion.

[0103] In the present application, the intensity of the ultraviolet light is controlled to be 10 mW / cm 2 -100 mW / cm 2 , which can ensure the curing of the three-dimensional structure material while constructing a uniform disordered surface wrinkle structure. If the intensity of the ultraviolet light is too low (e.g., the intensity of the ultraviolet light is 5 mW / cm 2), the curing degree on the surface of the three-dimensional structure material is low, resulting in low precision of the structure, and the three-dimensional structure material with the surface having the wrinkle structure cannot be obtained; if the intensity of the ultraviolet light is too high (for example, the intensity of the ultraviolet light is 150 mW / cm 2 ), the interlayer adhesion is poor, the structure of the three-dimensional structure material obtained is obviously layered, the printing precision of the overall structure is affected, and the high intensity of the ultraviolet light leads to too fast crosslinking speed of the system, which affects the gradient self-assembly of the fluorine-containing macromolecular photoinitiator on the surface of the material and makes it difficult to generate the wrinkle structure.

[0104] In a specific embodiment, in step (4), the above light crosslinking and curing treatment comprises: irradiating under ultraviolet light with a wavelength of 315 nm-400 nm and an intensity of 10 mW / cm 2 -100 mW / cm 2 for 5 min-20 min.

[0105] In a specific embodiment, in step (4), the above heat treatment has a temperature of 35℃-50℃ and a time of 30 min-90 min.

[0106] In a specific embodiment, the above multifunctional acrylate crosslinking agent is at least one of 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, glycerol trihydroxypropyl ether triacrylate, and pentaerythritol tetraacrylate.

[0107] In a specific embodiment, the above acrylate oligomer is at least one of polyether acrylate, aliphatic polyurethane triacrylate, and polyester acrylate.

[0108] The third aspect of the present application provides a three-dimensional structure material with a surface having a wrinkle structure, which is prepared by the above method for constructing a three-dimensional surface wrinkle structure. Compared with the problems of the surface wrinkle structure in the traditional three-dimensional structure material preparation, such as unadjustable surface wrinkle structure and difficult dynamic regulation, the present application introduces a synergistic construction mechanism of printing configuration and surface wrinkle structure, and simultaneously completes three-dimensional structure forming and surface micro-wrinkle structure generation in one step, without additional developing, washing and drying processes, thereby significantly reducing the processing complexity and environmental burden. In addition, the present application introduces a functional unit (graphene in the present embodiment) that responds to light / heat and other external stimuli into the formula of the raw material of the three-dimensional structure material, and gives the three-dimensional structure material the in-situ reversible dynamic regulation ability of the surface wrinkle structure, realizes the dynamic regulation of the surface wrinkle structure of the three-dimensional structure material, and effectively solves the problem that the surface of the traditional three-dimensional structure material is difficult to realize dynamic regulation, thereby providing a new way for constructing an integrated intelligent structure with sensing, responding and reconfigurable functions.

[0109] The present invention will be further described below through specific embodiments.

[0110] In the following examples, S5 polyether acrylate was purchased from Jiaxing Sudi Polymer Materials Co., Ltd., aliphatic polyurethane triacrylate was purchased from Jiaxing Sudi Polymer Materials Co., Ltd., 811 polyester acrylate was purchased from Zhanxin Resin Co., Ltd., and graphene was purchased from Aladdin Biochemical Technology Co., Ltd.

[0111] Example 1

[0112] This embodiment provides a fluorine-containing macromolecular photoinitiator I, the structural formula of which is as follows:

[0113]

[0114] Where x=10, y=30, z=10.

[0115] Figure 1 This is a synthetic route diagram of the fluorine-containing macromolecular photoinitiator I in Example 1 of the present invention, as shown below. Figure 1 As shown, the preparation method of the above-mentioned fluorine-containing macromolecular photoinitiator I provided in this embodiment includes the following steps:

[0116] (1) 40 mmol of dimethylaminoethyl methacrylate (DMAEMA), 10 mmol of perfluorooctyl ethyl acrylate, and 1 mmol of azobisisobutyronitrile (AIBN) were dissolved in 80 mL of 1,4-dioxane. The mixture was stirred at 80 °C for 18 h under a nitrogen atmosphere. The resulting mixture was precipitated in n-hexane, filtered, and a white precipitate was obtained. The white precipitate was then vacuum dried in a vacuum drying oven at 60 °C to obtain a white powdery random copolymer containing dimethylamino. The 1H NMR spectrum of this random copolymer containing dimethylamino is shown below. Figure 2 As shown.

[0117] (2) 40 mmol of the dimethylamino-containing random copolymer from step (1) and 20 mmol of 4-(bromomethyl)benzophenone were dissolved in 50 mL of N,N-dimethylformamide (DMF) and reacted at 70 °C for 24 h to prepare fluorinated macromolecular photoinitiator I. The proton NMR spectrum of this fluorinated macromolecular photoinitiator I is shown below. Figure 3 As shown.

[0118] Example 2

[0119] This embodiment provides a fluorine-containing macromolecular photoinitiator II, the structural formula of which is as follows:

[0120]

[0121] Where x=30, y=60, z=10.

[0122] Figure 4 For the synthesis route of the fluorine-containing macromolecular photoinitiator II in embodiment 2 of the present application, as shown in the following formula, the preparation method of the fluorine-containing macromolecular photoinitiator II provided in the present embodiment comprises the following steps: Figure 4

[0123] 30 mmol of dimethylaminoethyl methacrylate (DMAEMA), 60 mmol of 4-acryloyl hydroxybenzoic acid phenone, 10 mmol of perfluorooctyl ethyl acrylate and 1 mmol of azobisisobutyronitrile (AIBN) are dissolved in 80 mL of 1,4-dioxane, and the mixture is stirred at 80°C under nitrogen atmosphere for 18 h. The reaction mixture is precipitated in n-hexane, filtered to obtain white precipitate, and the white precipitate is vacuum dried in a vacuum drying box at 60°C to obtain white powder of the fluorine-containing macromolecular photoinitiator II. The proton nuclear magnetic resonance spectrum of the fluorine-containing macromolecular photoinitiator II is shown in the following formula. Figure 5

[0124] Embodiment 3

[0125] The present embodiment provides a method for constructing a three-dimensional surface wrinkle structure, comprising the following steps:

[0126] (1) 200 mg of the fluorine-containing macromolecular photoinitiator I in embodiment 1, 0.2 g of 1,6-hexanediol diacrylate, 0.2 g of pentaerythritol tetraacrylate and 0.5 g of S5 polyether acrylate are dissolved in 2 mL of chloroform solvent to prepare a 3D printing resin solution. The solid content mass percentage of the 3D printing resin solution is 27.1%, and the mass fraction of the fluorine-containing macromolecular photoinitiator I in the 3D printing resin solution is 4.9 wt%.

[0127] (2) The 3D printing resin solution is subjected to photocuring 3D printing according to a preset printing path (such as the a) of the following formula: Figure 6 Specifically, step S1, the 3D printing resin solution is extruded (the extrusion speed of the peristaltic pump is 5 mL / hr) through a printing nozzle with an inner diameter of 0.6 mm, and after reaching the stable extrusion state, the printing nozzle is controlled to move at a printing speed of 10 mm / s and is deposited on a polyethylene terephthalate (PET) substrate, while being combined with a 365 nm light source (ultraviolet light intensity is 60 mW / cm 2 ​​) The 3D printing resin solution is photo-crosslinking cured. Due to the funnel effect of light, the surface layer of the 3D printing resin solution is gradient crosslinked, which causes the mismatch of thermal expansion and shrinkage rates between the surface layer and the inner layer of the 3D printing resin solution. During the volatilization of the organic solvent and the cooling of the material, the shrinkage degree of the inner layer is higher than that of the surface layer, thereby forming a self- wrinkle structure in the surface layer, and obtaining a single-layer deposited material with a self- wrinkle structure on the surface (the printing thickness of each layer is 30 μm); step S2, repeating step S1, and finally stacking a three-dimensional structure material (thickness is 1.2 cm) through layer-by-layer deposition. The deposition system is controlled by a computer to move the printing nozzle in the x, y and z directions.

[0128] (3) The three-dimensional structure material is heat treated at 40°C for 1 h, and then subjected to photo-crosslinking curing treatment (irradiated for 10 min under a 365 nm ultraviolet light with an intensity of 60 mW / cm 2 2 of the present application. Figure 6

[0129] Example 4

[0130] The present embodiment provides a method for constructing a three-dimensional surface wrinkle structure, comprising the following steps:

[0131] (1) 200 mg of the fluorinated macromolecular photoinitiator II in Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glycerol trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate are dissolved in 2 mL of chloroform solvent to prepare a 3D printing resin solution; the solid content mass percentage of the 3D printing resin solution is 28.8%; the mass fraction of the fluorinated macromolecular photoinitiator II in the 3D printing resin solution is 4.8 wt%.

[0132] (2) The 3D printing resin solution is photo-cured 3D printed according to a preset printing path (such as Figure 7 (1) in the present application); specifically comprising: step S1, the 3D printing resin solution is extruded through a printing nozzle with an inner diameter of 0.6 mm (the extrusion speed of the peristaltic pump is 5 mL / hr), and after reaching the stable state of extrusion, the printing nozzle is controlled to move at a printing speed of 10 mm / s and deposited on a polyethylene terephthalate (PET) substrate, while combining a 365 nm light source (ultraviolet light intensity is 60 mW / cm 2 ​) and the inner layer shrinks to a greater extent than the surface layer during the evaporation of the organic solvent and the cooling of the material, thereby forming a self- wrinkle structure on the surface layer, obtaining a single-layer deposited material with a self- wrinkle structure on the surface (the printing thickness of each layer is 30 pm); step S2, repeating step S1, and finally stacking a three-dimensional structure material (thickness of 1.2 cm) through layer-by-layer deposition. The deposition system is controlled by a computer to move the printing nozzle in the x, y and z directions.

[0133] (3) The three-dimensional structure material is heated at 40°C for 1 h, and then subjected to photo-crosslinking curing treatment (irradiated for 10 min under a 365 nm ultraviolet light with an intensity of 60 mW / cm 2 Figure 7

[0134] Example 5

[0135] The embodiment provides a method for constructing a three-dimensional surface wrinkle structure, comprising the following steps:

[0136] (1) 300 mg of graphene is added to 10 mL of chloroform and ultrasonically dispersed for 36 h to prepare a graphene solution with a mass fraction of 2 wt%; 200 mg of the fluorine-containing macromolecular photoinitiator II in Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glyceryl trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate are mixed with 2 mL of the graphene solution to prepare a 3D printing resin solution; the solid content mass percentage of the 3D printing resin solution is 29.9%.

[0137] (2) The 3D printing resin solution is subjected to photo-curing 3D printing according to a preset printing path, specifically comprising: step S1, the 3D printing resin solution is extruded (the extrusion speed of the peristaltic pump is 5 mL / hr) through a printing nozzle with an inner diameter of 0.6 mm; after reaching a stable extrusion state, the printing nozzle is controlled to move at a printing speed of 10 mm / s and is deposited on a polyethylene terephthalate (PET) substrate, while a 365 nm light source (ultraviolet light intensity of 60 mW / cm 2 ​​) light cross-linking curing, due to the funnel effect of light, the surface layer of 3D printing resin solution is gradient cross-linked, which leads to the mismatch of thermal expansion and shrinkage rate between the surface layer and the inner layer of 3D printing resin solution, and in the process of organic solvent volatilization and material cooling, the shrinkage degree of the inner layer is higher than that of the surface layer, thereby forming a self- wrinkle structure in the surface layer, and a single-layer deposited material with a self- wrinkle structure on the surface (the printing thickness of each layer is 30 μm) is obtained; step S2, repeating step S1, and finally stacking a three-dimensional structure material (thickness is 1.2 cm) through layer-by-layer deposition.

[0138] (3) the three-dimensional structure material is heated at 40℃ for 1h, and then subjected to light cross-linking curing treatment (irradiated for 10 min under the ultraviolet light with a wavelength of 365 nm and an intensity of 60 mW / cm 2 Figure 8

[0139] Figure 8 Figure 1 is a schematic diagram of the in-situ dynamic regulation of the surface wrinkle structure of the three-dimensional structure material with a surface wrinkle structure in Example 5 of the present application; wherein, Figure 8 Figure 1a is a surface wrinkle structure diagram of the three-dimensional structure material with a surface wrinkle structure, Figure 8 Figure 1b is an enlarged view of the surface wrinkle structure of the three-dimensional structure material with a surface wrinkle structure, Figure 8 Figure 1c is a surface wrinkle structure diagram of the three-dimensional structure material with a surface wrinkle structure after irradiation with 808 nm near-infrared light, Figure 8 Figure 1d is an enlarged view of the surface wrinkle structure of the three-dimensional structure material with a surface wrinkle structure after irradiation with 808 nm near-infrared light.

[0140] Figure 2 is a schematic diagram of the in-situ dynamic regulation of the surface wrinkle structure of the three-dimensional structure material with a surface wrinkle structure in Example 6 of the present application; wherein, Figure 8 ​​It is evident that when the three-dimensional structural material with a wrinkled surface in this embodiment is irradiated with 808 nm near-infrared light, the wrinkled surface structure is erased. After the 808 nm near-infrared light irradiation is removed and the material is cooled to room temperature, the surface morphology spontaneously recovers to its initial shape, achieving in-situ restoration of the macroscopic structure and microscopic pattern. The inventors analyzed this and believe the reason is that, due to the excellent photothermal conversion effect of graphene, when the three-dimensional structural material with a wrinkled surface is irradiated with 808 nm near-infrared light, the system temperature of the three-dimensional structural material with a wrinkled surface rapidly increases, causing thermal expansion and erasing the wrinkled surface structure. After the 808 nm near-infrared light irradiation is removed, the system temperature decreases, causing volume contraction and leading to the restoration of the wrinkled surface structure. The above results indicate that the three-dimensional structural material with a wrinkled surface prepared in this embodiment has near-infrared response characteristics, achieving in-situ dynamic control of the three-dimensional surface wrinkled structure.

[0141] Comparative Example 1 (2 wt% of fluorine-containing macromolecular photoinitiator II in 3D printing resin solution)

[0142] The method for constructing the three-dimensional surface wrinkled structure provided in this comparative example is basically the same as that in Example 4, except that:

[0143] (1) Dissolve 80 mg of the fluorinated macromolecular photoinitiator II from Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glycerol trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate in 2 mL of chloroform solvent to prepare a 3D printing resin solution; the solid content of the 3D printing resin solution is 26.7% by mass; the mass fraction of the fluorinated macromolecular photoinitiator II in the 3D printing resin solution is 2 wt%.

[0144] Figure 9 This is a surface morphology diagram of the three-dimensional structural material in Comparative Example 1 of the present invention.

[0145] Depend on Figure 9 It can be seen that the surface of the three-dimensional structural material in this comparative example does not have disordered micron-level wrinkles. The inventors analyzed this and believe that the reason is that insufficient content of fluorine-containing macromolecular photoinitiator II leads to incomplete curing of the three-dimensional structural material, resulting in the inability to form wrinkles on the material surface.

[0146] Comparative Example 2 (20 wt% of fluorine-containing macromolecular photoinitiator II in 3D printing resin solution)

[0147] The method for constructing the three-dimensional surface wrinkled structure provided in this comparative example is basically the same as that in Example 4, except that:

[0148] (1) 1 g of the fluorine-containing macro-photoinitiator II in Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glyceryl trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate were dissolved in 2 mL of chloroform solvent to prepare a 3D printing resin solution; the solid content mass percentage of the 3D printing resin solution was 40.3%; the mass fraction of the fluorine-containing macro-photoinitiator II in the 3D printing resin solution was 20 wt%.

[0149] Figure 10 The surface morphology of the three-dimensional stereoscopic structure material in the present application Comparative Example 2 is shown in the figure.

[0150] It can be seen that the surface of the three-dimensional stereoscopic structure material in the present application Comparative Example 2 does not have a disordered micron-level wrinkle structure. The inventors analyzed the reason and believed that it was because the excessive fluorine-containing macro-photoinitiator II caused serious phase separation of the three-dimensional stereoscopic structure material, which resulted in the inability to build a disordered micron-level wrinkle structure on the surface of the material. Figure 10 Comparative Example 3 (the solid content mass percentage of the 3D printing resin solution was 10%)

[0151] The building method of the three-dimensional surface wrinkle structure provided in the present application Comparative Example 3 is basically the same as that in Example 4, except that:

[0152] (1) 200 mg of the fluorine-containing macro-photoinitiator II in Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glyceryl trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate were dissolved in 7.3 mL of chloroform solvent to prepare a 3D printing resin solution; the solid content mass percentage of the 3D printing resin solution was 10%.

[0153]

[0154] The physical picture of the three-dimensional stereoscopic structure material in the present application Comparative Example 3 is shown in the figure. Figure 11 It can be seen that the three-dimensional stereoscopic structure material in the present application Comparative Example 3 was not completely cured and formed. The inventors analyzed the reason and believed that it was because the solid content mass percentage of the 3D printing resin solution was too low, and its flowability was too high when extruded, which resulted in the inability to quickly cure and the difficulty in building a three-dimensional structure.

[0155] Figure 11 Comparative Example 4 (the solid content mass percentage of the 3D printing resin solution was 100%)

[0156] The building method of the three-dimensional surface wrinkle structure provided in the present application Comparative Example 4 is basically the same as that in Example 4, except that:

[0157]

[0158] ​​(1) 200 mg of fluorine-containing macromolecular photoinitiator II in Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glyceryl trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate, and 0.3 g of 811 polyester acrylate were thoroughly mixed to prepare a 3D printing resin solution; the solid content mass percentage of the 3D printing resin solution was 100%.

[0159] Figure 12 A physical picture of the three-dimensional structure material in the present application Comparative Example 4.

[0160] From the above, Figure 12 it can be seen that the three-dimensional structure material in the present comparative example was not completely cured and formed. The inventors analyzed the reason and believed that it was because the solid content mass percentage of the 3D printing resin solution was too high, and the resin fluidity was too low to be well extruded, resulting in low precision in the layer-by-layer accumulation printing process, and the three-dimensional structure material with uneven concave-convex and uneven thickness was prepared.

[0161] Comparative Example 5 (extrusion speed of 0.5 mL / hr)

[0162] The construction method of the three-dimensional surface wrinkle structure provided in the present comparative example is basically the same as that in Example 4, except that:

[0163] (2) the extrusion speed of the peristaltic pump of 5 mL / hr is replaced by the extrusion speed of the peristaltic pump of 0.5 mL / hr.

[0164] Figure 13 A surface topography of the three-dimensional structure material in the present application Comparative Example 5.

[0165] From the above, Figure 13 it can be seen that the surface of the three-dimensional structure material in the present comparative example does not have disordered micron-level wrinkle structure.

[0166] Comparative Example 6 (extrusion speed of 15 mL / hr)

[0167] The construction method of the three-dimensional surface wrinkle structure provided in the present comparative example is basically the same as that in Example 4, except that:

[0168] (2) the extrusion speed of the peristaltic pump of 5 mL / hr is replaced by the extrusion speed of the peristaltic pump of 15 mL / hr.

[0169] Figure 14 A surface topography of the three-dimensional structure material in the present application Comparative Example 6.

[0170] From the above, Figure 14 it can be seen that the surface of the three-dimensional structure material in the present comparative example does not have disordered micron-level wrinkle structure.

[0171] Comparative Example 7 (inner diameter of the printing nozzle is 0.2 mm)

[0172] The construction method of the three-dimensional surface wrinkle structure provided in the present comparative example is basically the same as that of Example 4, except that:

[0173] (2) the printing nozzle with an inner diameter of 0.6 mm is replaced by a printing nozzle with an inner diameter of 0.2 mm.

[0174] Figure 15 The surface topography of the three-dimensional structure material in Comparative Example 7 of the present application.

[0175] It can be seen that the surface of the three-dimensional structure material in the present comparative example has some uneven wrinkle structures oriented along the printing direction, which is not conducive to the subsequent application and mechanism exploration of disordered wrinkle structures. Figure 15

[0176] Comparative Example 8 (inner diameter of the printing nozzle is 1 mm)

[0177] The construction method of the three-dimensional surface wrinkle structure provided in the present comparative example is basically the same as that of Example 4, except that:

[0178] (2) the printing nozzle with an inner diameter of 0.6 mm is replaced by a printing nozzle with an inner diameter of 1 mm.

[0179] Figure 16 The surface topography of the three-dimensional structure material in Comparative Example 8 of the present application.

[0180] It can be seen that the surface of the three-dimensional structure material in the present comparative example has some uneven wrinkle structures oriented along the printing direction, which is not conducive to the subsequent application and mechanism exploration of disordered wrinkle structures. Figure 16

[0181] Comparative Example 9 (ultraviolet light intensity is 5 mW / cm 2 )

[0182] The construction method of the three-dimensional surface wrinkle structure provided in the present comparative example is basically the same as that of Example 4, except that:

[0183] (2) the ultraviolet light intensity of 60 mW / cm 2 is replaced by an ultraviolet light intensity of 5 mW / cm 2 .

[0184] (3) the irradiation under the ultraviolet light with a wavelength of 365 nm and an intensity of 60 mW / cm 2 for 10 min is replaced by the irradiation under the ultraviolet light with a wavelength of 365 nm and an intensity of 5 mW / cm 2 for 10 min.

[0185] ​​Figure 17 This is a surface morphology diagram of the three-dimensional structural material in Comparative Example 9 of the present invention.

[0186] Depend on Figure 17 It can be seen that no obvious wrinkles appeared on the surface of the three-dimensional structural material in this comparative example.

[0187] Comparative Example 10 (UV light intensity of 150 mW / cm²) 2 )

[0188] The method for constructing the three-dimensional surface wrinkled structure provided in this comparative example is basically the same as that in Example 4, except that:

[0189] (2) The intensity of ultraviolet light is 60mW / cm 2 Replace with ultraviolet light intensity of 150mW / cm 2 .

[0190] (3) At a wavelength of 365nm and an intensity of 60mW / cm 2 The 10-minute irradiation under ultraviolet light was replaced with irradiation at a wavelength of 365 nm and an intensity of 150 mW / cm. 2 Irradiate under ultraviolet light for 10 minutes.

[0191] Figure 18 This is a surface morphology diagram of the three-dimensional structural material in Comparative Example 10 of the present invention.

[0192] Depend on Figure 18 It can be seen that the surface of the three-dimensional material in this comparative example exhibits obvious layering and no wrinkled structure.

[0193] Comparative Example 11 (graphene solution with a mass fraction of 0.05 wt%)

[0194] The method for constructing the three-dimensional surface wrinkled structure provided in this comparative example is basically the same as that in Example 5, except that:

[0195] (1) 7.5 mg of graphene was added to 10 mL of chloroform and ultrasonically dispersed for 36 h to prepare a graphene solution with a mass fraction of 0.05 wt%. 200 mg of fluorine-containing macromolecular photoinitiator II from Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glycerol trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate were mixed with 2 mL of graphene solution to prepare a 3D printing resin solution. The solid content of the 3D printing resin solution was 28.8% by mass.

[0196] Figure 19 This is an in-situ dynamic control diagram of the surface wrinkle structure of the three-dimensional structural material with a wrinkled surface in Comparative Example 11 of the present invention, wherein...Figure 19 Figure a is a surface wrinkle structure diagram of the three-dimensional structural material with a wrinkled surface in Comparative Example 11 of the present invention. Figure 19 b is a diagram of the surface wrinkle structure of the three-dimensional structural material with a wrinkled surface in Comparative Example 11 of the present invention after being irradiated with 808nm near-infrared light.

[0197] Depend on Figure 19 It can be seen that when the three-dimensional structural material with a wrinkled surface in this comparative example is irradiated with 808nm near-infrared light, the wrinkled surface structure cannot be completely erased, and the in-situ dynamic control of the wrinkled surface structure cannot be achieved.

[0198] Comparative Example 12 (graphene solution with a mass fraction of 4 wt%)

[0199] The method for constructing the three-dimensional surface wrinkled structure provided in this comparative example is basically the same as that in Example 5, except that:

[0200] (1) 620 mg of graphene was added to 10 mL of chloroform and ultrasonically dispersed for 36 h to prepare a graphene solution with a mass fraction of 4 wt%. 200 mg of the fluorine-containing macromolecular photoinitiator II from Example 2, 0.2 g of trimethylolpropane trimethacrylate, 0.3 g of glycerol trihydroxypropyl ether triacrylate, 0.2 g of aliphatic polyurethane triacrylate and 0.3 g of 811 polyester acrylate were mixed with 2 mL of graphene solution to prepare a 3D printing resin solution. The solid content of the 3D printing resin solution was 38.1% by mass.

[0201] Figure 20 The image shows the surface wrinkle structure morphology of the three-dimensional structural material with a wrinkled surface in Comparative Example 12 of this invention.

[0202] Depend on Figure 20 It can be seen that the wrinkle structure on the surface of the three-dimensional material in this comparative example is not uniform.

[0203] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method of constructing a three-dimensional surface corrugation structure, characterized by, The method comprises the following steps: (1) dissolving a fluorine-containing macromolecular photoinitiator, a multifunctional acrylate crosslinking agent and an acrylate oligomer in an organic solvent to prepare a 3D printing resin solution, or mixing the fluorine-containing macromolecular photoinitiator, the multifunctional acrylate crosslinking agent, the acrylate oligomer and a graphene solution to prepare the 3D printing resin solution; (2) using light-curing 3D printing, allowing the 3D printing resin solution to be crosslinked and cured under light irradiation during printing and to be deposited on a substrate to obtain a single-layer deposited material with a self-pleated structure on the surface; (3) repeating step (2) to finally obtain a three-dimensional structure material by layer-by-layer deposition; (4) performing heat treatment and light crosslinking and curing treatment on the three-dimensional structure material to obtain a three-dimensional structure material with a pleated structure on the surface.

2. The method of claim 1, wherein the three-dimensional surface-ridged structure is formed by a method comprising: The structure of the fluorine-containing macromolecular photoinitiator is shown in formula (1) or formula (2): Formula (1) Formula (2) In formula (1) or formula (2), 0 < x ≤ 100, 0 < y ≤ 100, and 0 < z ≤ 100.

3. The method of claim 1 or 2, wherein In step (1), the mass fraction of the fluorine-containing macromolecular photoinitiator in the 3D printing resin solution is 4-15 wt%. And / or, in step (1), the mass ratio of the fluorine-containing macromolecular photoinitiator, the multifunctional acrylate crosslinking agent and the acrylate oligomer is (2-10):(5-50):(5-50).

4. The method for constructing a three-dimensional surface wrinkled structure according to claim 1, characterized in that, In step (1), the graphene solution is prepared by dissolving graphene in an organic solvent, and the mass fraction of the graphene solution is 0.2 wt%-2 wt%.

5. The method for constructing a three-dimensional surface wrinkled structure according to claim 1, characterized in that, In step (1), the solid content of the 3D printing resin solution is 20%-80%.

6. The method for constructing a three-dimensional surface wrinkled structure according to claim 1, characterized in that, In step (2), the process parameters of the light-curing 3D printing include: The extrusion speed of the peristaltic pump is controlled to be 1 mL / hr-10 mL / hr; The printing speed is controlled to be 5 mm / s-30 mm / s; The inner diameter of the printing nozzle is controlled to be 0.4 mm-0.8 mm; The printing thickness of each layer is controlled to be 10 μm-50 μm; The light conditions include: wavelength of 315-400 nm, intensity of 10 mW / cm 2 -100 mW / cm 2 ultraviolet light.

7. The method for constructing a three-dimensional surface wrinkled structure according to claim 1, characterized in that, In Step (4), the photo-crosslinking curing treatment includes irradiation with ultraviolet light having a wavelength of 315 nm to 400 nm and an intensity of 10 mW / cm 2 - 100 mW / cm 2 for 5 minutes to 20 minutes.

8. The method for constructing a three-dimensional surface wrinkled structure according to claim 1, characterized in that, In step (4), the temperature of the heat treatment is 35℃-50℃, and the time is 30 min-90 min.

9. The method for constructing a three-dimensional surface wrinkled structure according to claim 1, characterized in that, The multifunctional acrylate crosslinking agent is at least one of 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, glycerol trihydroxypropyl ether triacrylate and pentaerythritol tetraacrylate; And / or, the acrylate oligomer is at least one of polyether acrylate, aliphatic polyurethane triacrylate and polyester acrylate.

10. A three-dimensional structural material with a wrinkled surface, characterized in that, The three-dimensional surface pleated structure is prepared by the method of any one of claims 1-9.

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