阅读说明：本技术 一种光热双响应的形状记忆材料及其制备方法和用途 (Photo-thermal dual-response shape memory material and preparation method and application thereof ) 是由 张爱民 唐蝶 于 2021-09-23 设计创作，主要内容包括：本发明提供了一种光热双响应的类玻璃体形状记忆材料,它由如下质量比例份数的原料制备而成：环氧基封端的单体0.2～1.0份、环氧树脂1.5～2.5份、交联剂3.2～5.2份；所述交联剂为2～3个巯基的化合物或低聚物,或其组合。本发明材料在保持高热稳定性、耐溶剂性、高机械性能和可修复性能等优异性能的同时,能够借助光能转换成热能的能力,从而诱导材料发生形状的变化。与大多数基于热响应的形状记忆聚合物相比,本发明材料由于能够实现无接触式的、远程的、局部精确的控制,使其在智能材料领域具有广泛的应用价值和潜力。(The invention provides a photo-thermal dual-response glass-like shape memory material which is prepared from the following raw materials in parts by mass: 0.2-1.0 part of epoxy-terminated monomer, 1.5-2.5 parts of epoxy resin and 3.2-5.2 parts of cross-linking agent; the cross-linking agent is a compound or oligomer with 2-3 sulfydryl groups, or a combination thereof. The material of the invention can induce the shape change of the material by virtue of the capability of converting light energy into heat energy while maintaining excellent performances such as high thermal stability, solvent resistance, high mechanical property, repairability and the like. Compared with most of shape memory polymers based on thermal response, the material disclosed by the invention has wide application value and potential in the field of intelligent materials due to the fact that the material can realize non-contact, remote and local precise control.)

1. The photo-thermal dual-response shape memory material is prepared from the following raw materials in parts by mass:

0.2-1.0 part of epoxy-terminated monomer, 1.5-2.5 parts of epoxy resin and 3.2-5.2 parts of cross-linking agent;

the epoxy-terminated monomer structure is as follows:

the crosslinking agent is a compound or oligomer containing 2-3 sulfydryl groups, or a combination thereof.

2. The shape memory material of claim 1, wherein the raw materials comprise, by weight: 0.2 part of epoxy-terminated monomer, 2.0 parts of epoxy resin and 3.2 parts of cross-linking agent.

3. The shape memory material according to claim 1 or 2, wherein the crosslinking agent is a combination of a polysulfide oligomer and a dithiol compound, and the mass ratio of the polysulfide oligomer and the dithiol compound is (5-28): 1.

4. A shape memory material in accordance with claim 3 wherein said polysulfide oligomer is a liquid polysulfide rubber; the dithiol compound is 2,2' - (1, 2-ethanediylbis oxo) bisethanethiol.

5. The shape memory material of claim 4, wherein said liquid polysulfide rubber is at least one of LP, LP23, LP2, G44, G4.

6. Shape memory material according to claim 1 or 2, characterized in that the epoxy resin is a bisphenol a type epoxy resin.

7. Shape memory material according to claim 6, characterized in that the epoxy resin is one of the epoxy resins of type E54, E51, E44, E42, preferably E51.

8. A method of preparing a shape memory material according to any of claims 1 to 7, comprising the steps of:

(1) dissolving and uniformly mixing all raw materials and a catalyst in an organic solvent to obtain a mixture;

(2) and (3) reacting and curing the mixture at 50-85 ℃ for 8-24 h, and removing the organic solvent to obtain the organic silicon-aluminum-zinc-aluminum composite material.

9. The method according to claim 8, wherein the catalyst in step (1) is a tertiary amine catalyst, preferably 2,3, 4-tris (dimethylaminomethyl) phenol; the mass fraction of the added catalyst is 1-8 wt%;

the organic solvent is at least one of acetone, tetrahydrofuran, N-dimethylformamide and xylene.

10. Use of the shape memory material of any one of claims 1 to 7 in smart materials, including biomimetic animals, plants, biomimetic robots, smart electronic devices.

Technical Field

The invention belongs to the field of materials, and particularly relates to a photo-thermal dual-response shape memory material, and a preparation method and application thereof.

Background

The intelligent material is a novel functional material which can sense external stimulation, can judge and appropriately process and can be executed. In recent years, smart materials have been developed very rapidly, and shape memory polymer materials (SMPs), as one of them, have been widely researched and focused. SMPs can be transformed from one shape to another shape upon sensing external environmental stimuli, and find applications in many fields, such as smart textile materials in the textile field, heat-shrinkable packaging materials in sensors in the electronic engineering field, biomedical device materials or smart medical device materials, high performance water and vapor permeable materials in household products, self-expandable materials on spacecraft in the aerospace field, and the like.

Thermotropic shape memory polymers are the most common kind of SMPs, but the function thereof is relatively single and cannot meet the complex requirements of special environments (such as instantaneous, remote and local control), so that the function which is different from the shape memory performance and the response characteristic which is other than the thermal response performance are often required to be endowed by introducing a functional unit. For example, a photoresponsive group is introduced, so that remote, local and accurate control can be realized under the condition that light does not contact an object, point-to-point regulation and control are realized, light energy is converted into mechanical energy through regulating and controlling illumination, shape deformation occurs, and the advantages of the thermotropic shape memory material are further expanded. However, at present, most of the ways of introducing the functional units are doping blending, but the compatibility with the matrix material itself is not good, and the overall performance of the material is necessarily adversely affected. Meanwhile, most of the shape memory materials with functional units and multiple responses are thermoplastic systems, and the crosslinked thermosetting systems usually limit the chain segment movement, so that the shape memory performance of the materials is reduced. However, the materials of thermoplastic systems have the problems of poor mechanical properties and poor solvent resistance. Therefore, it is often difficult to achieve excellent shape memory properties, mechanical properties, and solvent resistance.

How to properly introduce functional units to obtain a shape memory material with multiple responses and enable the material to have comprehensive properties such as excellent mechanical properties, solvent resistance and the like, and the application of the material as an intelligent material is widened, and still needs to be further researched.

Disclosure of Invention

The invention aims to provide a photo-thermal dual-response shape memory material.

The invention provides a photo-thermal dual-response shape memory material which is prepared from the following raw materials in parts by mass:

0.2-1.0 part of epoxy-terminated monomer, 1.5-2.5 parts of epoxy resin and 3.2-5.2 parts of cross-linking agent;

the epoxy-terminated monomer structure is as follows:

the cross-linking agent is a compound or oligomer with 2-3 sulfydryl groups, or a combination thereof.

Further, the raw materials comprise the following components in parts by weight: 0.2 part of epoxy-terminated monomer, 2.0 parts of epoxy resin and 3.2 parts of cross-linking agent.

The crosslinking agent is a combination of a polysulfide oligomer and a dithiol compound, and the mass ratio of the polysulfide oligomer to the dithiol is (5-28): 1.

Further, the polysulfide oligomer is a liquid polysulfide rubber; the dithiol compound is 2,2' - (1, 2-ethanediylbis oxo) bisethanethiol.

Preferably, the liquid polysulfide rubber is at least one of LP, LP23, LP2, G44 and G4.

Further, the epoxy resin is a bisphenol a type epoxy resin.

Preferably, the epoxy resin is one of epoxy resins of E54, E51, E44 and E42 types, and is preferably an epoxy resin of E51 type.

The invention also provides a preparation method of the shape memory material, which comprises the following steps:

(1) dissolving and uniformly mixing all raw materials and a catalyst in an organic solvent to obtain a mixture;

(2) and (3) reacting and curing the mixture at 50-85 ℃ for 8-24 h, and removing the organic solvent to obtain the organic silicon-aluminum-zinc-aluminum composite material.

Further, the catalyst in the step (1) is a tertiary amine catalyst, preferably 2,3, 4-tris (dimethylaminomethyl) phenol; the mass fraction of the added catalyst is 1-8 wt%;

the organic solvent is at least one of acetone, tetrahydrofuran, N-dimethylformamide and xylene.

The invention also provides the application of the shape memory material in intelligent materials, wherein the intelligent materials comprise bionic animals, plants, bionic robots and intelligent electronic equipment.

The invention has the beneficial effects that: the functional groups are directly and covalently connected into the molecular chain of the material, so that the problems of agglomeration incompatibility and the like are avoided, and the overall performance is not adversely affected, so that the material can be induced to change in shape by virtue of the capability of converting light energy into heat energy while maintaining excellent performances such as high thermal stability, solvent resistance, high mechanical property, repairability and the like. Compared with most of shape memory polymers based on thermal response, the material disclosed by the invention can realize non-contact, remote and local precise control, can restore a complex three-dimensional shape to an original shape under the condition of heating or ultraviolet irradiation, can design and prepare various drivers with complex shapes and appearances through reasonable shape design, is used for a gripper robot or bionic plants and other products, and has wide application value and potential in the field of intelligent materials.

Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.

The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Drawings

FIG. 1 is a diagram illustrating the verification of the shape memory effect of the shape memory material according to the present invention in response to light and heat.

FIG. 2 shows the DMA test results of the shape memory material of the present invention.

FIG. 3 illustrates the thermal conversion effect of the shape memory material of the present invention under UV light.

FIG. 4 shows the results of testing the solvent resistance of the shape memory material of the present invention (1 is DMF, 2 is acetone, 3 is dichloromethane, 4 is chloroform, and 5 is toluene).

Detailed Description

The raw materials used in the invention are as follows: 4-nitrobenzoic acid, liquid polysulfide oligomer with reactive thiol end groups (thioplast G4, Mn <1100G/mol), glucose, sodium hydroxide, 3, 6-dioxaoctane-1, 8-dithiol, acetic acid, N-Dimethylformamide (DMF), potassium carbonate, catalyst: 2,4, 6-tris (dimethylaminomethyl) phenol, which is a known product, is obtained by purchasing a commercially available product.

Epoxy-terminated azobenzene structure-containing monomer (EAZO):prepared according to the following literature. [1]Zhang L,et al.Multidirectional biomimetic deformation of microchannel programmed metal nanowire liquid crystal networks[J].Journal of Materials Chemistry C,2019,7.

[2]Liu B W,et al.Novel crosslinkable epoxy resins containing phenylacetylene and azobenzene groups:From thermal crosslinking to flame retardance[J].Polymer Degradation and Stability,2015,122:66-76.

EXAMPLE 1 preparation of shape memory Material of the invention

0.4G of EAZO, 2.0G of epoxy resin E51, 3G of liquid polysulfide rubber G4 and 0.2G of 2,2' - (1, 2-ethanediylbenzoyloxy) bisethanethiol are dissolved in 30mL of DMF, stirred uniformly, mixed and dissolved, 0.2G of catalyst 2,3, 4-tris (dimethylaminomethyl) phenol (DMP-30)) is added, and stirred uniformly. And (3) placing the completely uniform mixture in a polytetrafluoroethylene template, curing for 6h at 50 ℃, then heating to 85 ℃, curing and reacting for 6h, placing in an oven, and evaporating the organic solvent to obtain the intelligent shape memory polymer material capable of generating shape change under ultraviolet irradiation and heating.

Example 2 preparation of the Material of the invention

0.4G of EAZO, 2.0G of epoxy resin E51, 3G of liquid polysulfide rubber G4 and 0.4G of 2,2' - (1, 2-ethanediylbenzoyloxy) bisethanethiol are dissolved in 30mL of DMF, stirred uniformly, mixed and dissolved, 0.2G of catalyst 2,3, 4-tris (dimethylaminomethyl) phenol (DMP-30)) is added, and stirred uniformly. And (3) placing the completely uniform mixture in a polytetrafluoroethylene template, curing for 6h at 50 ℃, then heating to 85 ℃, curing and reacting for 6h, placing in an oven, and evaporating the organic solvent to obtain the intelligent shape memory polymer material capable of generating shape change under ultraviolet irradiation and heating.

Example 3 preparation of the Material of the invention

0.6G of EAZO, 2.0G of epoxy resin E51, 4G of liquid polysulfide rubber G4 and 0.4G of 2,2' - (1, 2-ethanediylbenzoyloxy) bisethanethiol are dissolved in 30mL of DMF, stirred uniformly, mixed and dissolved, 0.3G of catalyst 2,3, 4-tris (dimethylaminomethyl) phenol (DMP-30)) is added, and stirred uniformly. And (3) placing the completely uniform mixture in a polytetrafluoroethylene template, curing for 6h at 50 ℃, then heating to 85 ℃, curing and reacting for 6h, placing in an oven, and evaporating the organic solvent to obtain the intelligent shape memory polymer material capable of generating shape change under ultraviolet irradiation and heating.

Example 4 preparation of the Material of the invention

0.8G of EAZO, 2.0G of epoxy resin E51, 4.5G of liquid polysulfide rubber G4 and 0.4G of 2,2' - (1, 2-ethanediylbis-oxo) bisethanethiol are dissolved in 30mL of DMF, stirred uniformly, mixed and dissolved, 0.35G of catalyst 2,3, 4-tris (dimethylaminomethyl) phenol (DMP-30)) is added, and stirred uniformly. And (3) placing the completely uniform mixture in a polytetrafluoroethylene template, curing for 6h at 50 ℃, then heating to 85 ℃, curing and reacting for 6h, placing in an oven, and evaporating the organic solvent to obtain the intelligent shape memory polymer material capable of generating shape change under ultraviolet irradiation and heating.

Example 5 preparation of the Material of the invention

1.0G of EAZO, 2.0G of epoxy resin E51, 5G of liquid polysulfide rubber G4 and 0.2G of 2,2' - (1, 2-ethanediylbenzoyloxy) bisethanethiol are dissolved in 30mL of DMF, stirred uniformly, mixed and dissolved, 0.35G of catalyst 2,3, 4-tris (dimethylaminomethyl) phenol (DMP-30)) is added, and stirred uniformly. And (3) placing the completely uniform mixture in a polytetrafluoroethylene template, curing for 6h at 50 ℃, then heating to 85 ℃, curing and reacting for 6h, placing in an oven, and evaporating the organic solvent to obtain the intelligent shape memory polymer material capable of generating shape change under ultraviolet irradiation and heating.

Example 6 preparation of the Material of the invention

0.2G of EAZO, 2.0G of epoxy resin E51, 3.5G of liquid polysulfide rubber G4 and 0.4G of 2,2' - (1, 2-ethanediylbis-oxo) bisethanethiol are dissolved in 30mL of DMF, stirred uniformly, mixed and dissolved, 0.25G of catalyst 2,3, 4-tris (dimethylaminomethyl) phenol (DMP-30)) is added and stirred uniformly. And (3) placing the completely uniform mixture in a polytetrafluoroethylene template, curing for 6h at 50 ℃, then heating to 85 ℃, curing and reacting for 6h, placing in an oven, and evaporating the organic solvent to obtain the intelligent shape memory polymer material capable of generating shape change under ultraviolet irradiation and heating.

The beneficial effects of the material of the invention are demonstrated by the following experimental examples.

Experimental example 1 characterization of photo-thermal response Properties of the Material of the invention

1. Photothermal response shape memory performance

Figure 1 visually shows that the material of the invention (example 1) can excite the shape memory property under the heating condition and the 365nm ultraviolet irradiation condition, so that the programmed temporary shape is restored to the original shape, and the photo-thermal response shape memory property of the material of the invention is verified.

The material prepared in example 1 was subjected to a dynamic thermo-mechanical analysis (DMA) test, and the result is shown in fig. 2, which shows that the material of the present invention has excellent shape memory properties, and both the shape fixation rate and the shape recovery rate are higher than 80%.

Further, the material prepared in example 1 was irradiated under 365nm ultraviolet light, and pictures were taken by an infrared thermal imager, and the results are shown in fig. 3, which shows that the material of the present invention has a rapid photothermal conversion efficiency, and the temperature can be raised from about 30 ℃ to more than 80 ℃ within 60 s; the temperature can be further increased to above 112.5 ℃ within 142 s.

Therefore, the material can convert light energy into heat energy through 365nm ultraviolet irradiation, and further excites the shape memory performance to cause shape transformation.

2. Solvent resistance

As shown in FIG. 4, in the figure, 1 is DMF, 2 is acetone, 3 is dichloromethane, 4 is trichloromethane, and 5 is toluene solvent, and the results show that after the material of the example 1 of the invention is soaked in the organic solvent for 48 hours, no obvious dissolution and destruction change occurs, which shows that the material of the invention has excellent solvent resistance, good stability and wide application field.

In summary, the present invention provides a photo-thermal dual-response shape memory material, which can induce the shape change of the material by virtue of the ability of converting light energy into heat energy while maintaining excellent properties such as high thermal stability and solvent resistance. Compared with most of shape memory polymers based on thermal response, the material disclosed by the invention has wide application value and potential in the field of intelligent materials due to the fact that the material can realize non-contact, remote and local precise control.