A thermally driven shape memory polymer ceramic material and its preparation method and application

Abstract

The present invention provides a thermally driven shape memory polymer ceramic material, its preparation method, and application, relating to the technical field of ceramic materials. The method for preparing the thermally driven shape memory polymer ceramic material provided by the present invention comprises the following steps: mixing an acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano-zirconium oxide, and a photoinitiator, and conducting a polymerization reaction to obtain the thermally driven shape memory polymer ceramic material. The thermally driven shape memory polymer ceramic material prepared by the present invention can achieve shape memory and recovery through temperature changes, exhibits excellent deformation properties for 4D printing, and is suitable for 4D printing.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic materials, and in particular to a thermally driven shape memory polymer ceramic material and a preparation method and application thereof. Background Art

[0002] Existing 4D-printed ceramics use prestressing to deform ceramic elastomers. After sintering, the shape is fixed and cannot deform. However, practical applications often require ceramic structures to be deformable even after sintering. Therefore, the idea is to use printed liquid crystal elastomers as a driving force to design deformable ceramic structures. Summary of the Invention

[0003] The purpose of the present invention is to provide a thermally driven shape memory polymer ceramic material and its preparation method and application. The thermally driven shape memory polymer ceramic material prepared by the present invention can achieve shape memory and recovery through temperature changes, has excellent 4D printing deformation characteristics, and can realize 4D printing.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a thermally driven shape memory polymer ceramic material, comprising the following steps:

[0006] Acrylate monomers, polycaprolactone, polyethylene glycol diacrylate, nano zirconium oxide and a photoinitiator are mixed and polymerized to obtain a thermally driven shape memory polymer ceramic material.

[0007] Preferably, the mass ratio of the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate and initiator is 6-12:1-5:3-9:0.1; the mass ratio of the nano zirconium oxide and the acrylate monomer is 17-23:6-12.

[0008] Preferably, the acrylic acid ester monomer includes one or both of butyl acrylate and tert-butyl acrylate.

[0009] Preferably, the photoinitiator is an acylphosphine oxide photoinitiator.

[0010] Preferably, the mixing of the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano zirconium oxide and photoinitiator comprises: first mixing the acrylate monomer and part of the polycaprolactone, then adding the remaining polycaprolactone for second mixing, then adding polyethylene glycol diacrylate for third mixing, and finally adding nano zirconium oxide and photoinitiator for fourth mixing.

[0011] Preferably, the polymerization reaction is carried out under ultraviolet light irradiation.

[0012] Preferably, the wavelength of the ultraviolet light is 405 nm; the intensity of the ultraviolet light is 3200-3600 μW / cm2.

[0013] The present invention provides a thermally driven shape memory polymer ceramic material prepared by the preparation method described in the above technical solution.

[0014] The present invention provides the use of the thermally driven shape memory polymer ceramic material described in the above technical solution as a 4D printing material.

[0015] The present invention provides a method for preparing a thermally driven shape memory polymer ceramic material, comprising the following steps: mixing an acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano zirconium oxide, and a photoinitiator, and performing a polymerization reaction to obtain a thermally driven shape memory polymer ceramic material. When the temperature rises to the crystallization phase transition temperature of polycaprolactone, the polymer ceramic material can be fixed in shape at zero time. After cooling, the polycaprolactone recrystallizes, wrapping the ceramic particles inside the polymer, and the overall structure maintains the zero-time shape. When the temperature is raised again to the crystallization phase transition temperature of polycaprolactone, the crystals melt, and the polymer returns to its original shape. The thermally driven shape memory polymer ceramic material prepared by the present invention can achieve shape memory and recovery through temperature changes, has excellent 4D printing deformation characteristics, and can realize 4D printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a graph showing the shape memory performance test results of the resin prepared for the verification example; Figure 1 a is the cured resin, b is the process of bending the resin at room temperature, c is the result of bending at room temperature and then releasing it to restore it to its original shape, and d is the result of bending the resin by heating and then releasing it;

[0017] Figure 2 This is a physical image of the spline printed in Example 2;

[0018] Figure 3 This is the effect diagram of the material printed in Example 2 after folding; Figure 3 a is the printed material, b is the heating and folding process, and c is the shape after folding. DETAILED DESCRIPTION

[0019] The present invention provides a method for preparing a thermally driven shape memory polymer ceramic material, comprising the following steps:

[0020] Acrylate monomers, polycaprolactone, polyethylene glycol diacrylate, nano zirconium oxide and a photoinitiator are mixed and polymerized to obtain a thermally driven shape memory polymer ceramic material.

[0021] In the present invention, the mass ratio of the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate and photoinitiator is preferably 6-12:1-5:3-9:0.1, more preferably 9:1.26:6:0.1; the mass ratio of the nano zirconium oxide and the acrylate monomer is preferably 17-23:6-12, more preferably 20:9.

[0022] In the present invention, the acrylic ester monomer preferably includes one or both of butyl acrylate and tert-butyl acrylate.

[0023] In the present invention, the average particle size of the nano-zirconia is preferably 200-900 nm, more preferably 750 nm.

[0024] In the present invention, the photoinitiator is preferably an acylphosphine oxide photoinitiator, more preferably diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO).

[0025] In the present invention, the mixing of the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano-zirconia, and a photoinitiator preferably includes: a first mixing of the acrylate monomer and a portion of the polycaprolactone, followed by a second mixing of the remaining polycaprolactone, a third mixing of the polyethylene glycol diacrylate, and finally a fourth mixing of the nano-zirconia and the photoinitiator. In the present invention, the temperatures for the first and second mixing steps are each preferably 50°C to 80°C, more preferably 50°C. The mass ratio of the portion of the polycaprolactone to the remaining polycaprolactone is preferably 1:0.26-1. In the present invention, the stepwise addition of the polycaprolactone can promote its dissolution.

[0026] In the present invention, the polymerization reaction is preferably carried out under ultraviolet light. The wavelength of the ultraviolet light is preferably 405 nm; the intensity of the ultraviolet light is preferably 3200-3600 μW / cm², more preferably 3400 μW / cm²; and the distance between the ultraviolet light and the reactants is preferably 120 mm. During the polymerization reaction, the photoinitiator causes the double-bonded monomers and crosslinkers in the system to open their double chains, resulting in crosslinking and encapsulating the ceramic particles in the system.

[0027] In the present invention, the thermally driven shape memory polymer ceramic material is printable.

[0028] The present invention also provides a thermally actuated shape-memory polymer ceramic material prepared by the preparation method described in the above technical solution. In the present invention, the thermally actuated shape-memory polymer ceramic material can return to its original shape after being bent at room temperature and then released; and after being bent by heating, its bent shape can be maintained. In the present invention, the heating temperature is preferably 50-65°C. The thermally actuated shape-memory polymer ceramic material provided by the present invention has excellent shape memory and recovery properties, and can also be adjusted in shape through temperature changes.

[0029] The present invention also provides the use of the thermally driven shape memory polymer ceramic material described in the above technical solution as a 4D printing material, preferably for the preparation of flexible electronic products. In the present invention, the method of application preferably includes: mixing an acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano-zirconia, and a photoinitiator to obtain a slurry; and printing the slurry to obtain the thermally driven shape memory polymer ceramic material. In the present invention, the parameters for mixing the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano-zirconia, and photoinitiator are consistent with those described above and are not further described here. In the present invention, the printing parameters preferably include: a UV light wavelength of preferably 405 nm; a UV light intensity of preferably 3200 to 3600 μW / cm², more preferably 3400 μW / cm²; an exposure time for the first layer of preferably 4 to 16 seconds, more preferably 10 seconds; and an exposure time for the remaining layers of preferably 1 to 12 seconds, more preferably 6 seconds.

[0030] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0031] Example 1

[0032] 9g of butyl acrylate (BA) and 1g of polycaprolactone (PCL) were dissolved at 50°C, 0.26g of PCL was added and heated with stirring to dissolve the PCL; the solution was allowed to stand overnight until it became clear and transparent; 6g of polyethylene glycol diacrylate (PEGDA) was added and the solution became clear and transparent after stirring; 0.1g of TPO and 20g of nano-zirconia with an average particle size of 750nm were added and cured in a UV curing oven with a wavelength of 405nm, an intensity of 3400μW / cm2, and a distance of 120mm between the UV light and the reactants to obtain a strip-shaped thermally driven shape memory polymer ceramic material.

[0033] Example 2

[0034] Dissolve 9g of butyl acrylate (BA) and 1g of polycaprolactone (PCL) at 50°C, add 0.26g of PCL, heat and stir to dissolve the PCL; let it stand overnight until the solution becomes clear and transparent; add 6g of polyethylene glycol diacrylate (PEGDA), and stir until the solution becomes clear and transparent; add 0.1g of TPO and 20g of nano-zirconia with an average particle size of 750nm to obtain a slurry.

[0035] The slurry is printed using a DLP device to obtain the following Figure 2 The thermally driven shape memory polymer ceramic material with regular shape shown in the figure was printed by the Chuangxiang 3D DP-002 printer with the following printing parameters: UV wavelength of 405nm, UV intensity of 3400μW / cm2, first layer exposure of 10s, and other layers exposure of 6s.

[0036] The slurry was printed using a DLP device. The printer model was Chuangxiang 3D DP-002. The printing parameters were: the wavelength of the ultraviolet light was 405 nm, the intensity of the ultraviolet light was 3400 μW / cm2, the first layer was exposed for 10 seconds, and the remaining layers were exposed for 6 seconds. Figure 3 The thermally driven shape memory polymer ceramic material of the shape shown in a is heated to 60°C and folded and fixed to obtain the following Figure 3 The product is in the shape shown in c. This shows that the thermally driven shape memory polymer ceramic material prepared by the present invention can be applied to flexible electronic materials with changing shapes, and can also be used as a flexible driving material.

[0037] Verification Example

[0038] The preparation method is basically the same as that of Example 1, except that nano-zirconia is not added and the prepared resin is transparent, to verify whether the prepared resin has shape memory properties.

[0039] The cured strips of resin were heated in hot water at 60°C and then fixed into another shape, showing that they have a certain shape-retaining function.

[0040] like Figure 1 As shown in the figure, the strip resin will return to its original shape after being fixed for a long time at room temperature. However, after being fixed by hot air heating to 60℃, its curved shape can be well maintained.

[0041] After adding nano-zirconia, the heat-driven shape memory polymer ceramic material prepared using the raw materials of Example 1 was verified to have good shape memory and recovery properties, and the shape can be adjusted by temperature changes.

[0042] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a thermally actuated shape memory polymer ceramic material, comprising the following steps: Mixing acrylate monomers, polycaprolactone, polyethylene glycol diacrylate, nano zirconium oxide and a photoinitiator, and performing a polymerization reaction to obtain a thermally driven shape memory polymer ceramic material; The acrylic ester monomer includes one or both of butyl acrylate and tert-butyl acrylate; the average particle size of the nano zirconium oxide is 200 to 900 nm; The mass ratio of the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate and photoinitiator is 6-12:1-5:3-9:0.1; the mass ratio of the nano zirconium oxide and the acrylate monomer is 17-23:6-12.

2. The preparation method according to claim 1, characterized in that The photoinitiator is an acylphosphine oxide photoinitiator.

3. The preparation method according to claim 1, characterized in that The mixing of the acrylate monomer, polycaprolactone, polyethylene glycol diacrylate, nano zirconium oxide and photoinitiator comprises: first mixing the acrylate monomer and part of the polycaprolactone, then adding the remaining polycaprolactone for second mixing, then adding polyethylene glycol diacrylate for third mixing, and finally adding nano zirconium oxide and photoinitiator for fourth mixing.

4. The preparation method according to claim 1, characterized in that The polymerization reaction is carried out under ultraviolet light irradiation.

5. The preparation method according to claim 4, characterized in that The wavelength of the ultraviolet light is 405nm; the intensity of the ultraviolet light is 3200-3600μW / cm 2 .

6. The thermally driven shape memory polymer ceramic material prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the thermally driven shape memory polymer ceramic material according to claim 6 as a 4D printing material.

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