阅读说明：本技术 一种增强型多重刺激光固化3d打印形状记忆材料及其制备方法 (Enhanced multi-thorn laser curing 3D printing shape memory material and preparation method thereof ) 是由 单武斌 陈雷 刘鹏 周亮 黄小琦 颜成龙 蒋国云 肖湘彬 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种增强型多重刺激光固化3D打印形状记忆材料及其制备方法,由环氧树脂丙烯酸酯、甲基丙烯酸-2-羟基乙酯、二丙二醇二丙烯酸酯、光引发剂、改性无机填料、经处理的鱼鳞软质层等组成；本发明经过多种刺激完成形状记忆过程,并且经过力学性能增强后其形状记忆恢复速度加快,仅需十几秒钟即可完成整个形状记忆过程,结合光固化3D打印在医学上应用的血管支架、无源控制的柔性机器人、家用智能开关方面进行应用。本发明制备方法生产周期短,成本低,省时省力,易于工业化生产。(The invention discloses an enhanced multi-prick laser curing 3D printing shape memory material and a preparation method thereof, wherein the material comprises epoxy resin acrylate, 2-hydroxyethyl methacrylate, dipropylene glycol diacrylate, a photoinitiator, modified inorganic filler, a treated fish scale soft layer and the like; the shape memory process is completed through various stimulations, the shape memory recovery speed is accelerated after the mechanical property is enhanced, the whole shape memory process can be completed in only ten seconds, and the photocuring 3D printing is combined to be applied to blood vessel supports applied in medicine, passive control flexible robots and household intelligent switches. The preparation method has the advantages of short production period, low cost, time and labor saving and easy industrial production.)

1. The utility model provides an enhancement mode multiple thorn laser solidification 3D prints shape memory material which characterized in that: the composite material is prepared from the following raw materials in parts by mass:

epoxy resin acrylate: 20-70 parts of a solvent;

30-60 parts of 2-hydroxyethyl methacrylate;

10-30 parts of dipropylene glycol diacrylate

1-5 parts of a photoinitiator;

0.05-3 parts of modified inorganic filler;

soft layer of the treated fish scales: 1-5 parts.

2. The enhanced multi-stimulus laser-cured 3D printed shape memory material of claim 1, wherein: the photoinitiator is at least one of photoinitiator 819, photoinitiator TPO, photoinitiator 184, photoinitiator 784 or photoinitiator ITX.

3. The enhanced multi-stimulus laser-cured 3D printed shape memory material of claim 1, wherein: the modified inorganic filler is at least one of carbon black, carbon nano tubes, graphene oxide, MXene or polydopamine, and is subjected to surface modification treatment by a silane coupling agent.

4. The enhanced multi-stimulus laser-cured 3D printed shape memory material of claim 1, wherein: the scale of the processed scale soft layer is at least one of grass carp scale, goldfish scale or black carp scale.

5. A preparation method of an enhanced multi-prick laser curing 3D printing shape memory material is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) synthesis of epoxy resin acrylate: adding 500-600mL butanone solvent into a three-neck flask, adding 50-60 parts by mass of epoxy resin and 15-20 parts by mass of acrylic acid, stirring until the epoxy resin and the acrylic acid are completely dissolved, adding 0.01-0.02 part by mass of triethylamine catalyst and 0.005-0.01 part by mass of 2, 6-di-tert-butyl p-cresol polymerization inhibitor, controlling the reaction temperature to be 90-100 ℃ under the nitrogen protection atmosphere, cooling the temperature to 55-70 ℃ after the reaction is completely finished, discharging, and naturally cooling in the air to obtain epoxy resin acrylate;

(2) preparation of the treated soft layer of fish scales: soaking 1-5 parts by mass of fish scales in an acetic acid solution for 2-6min, removing a calcium layer of the fish scales, completely freezing the soaked fish scales at-20 ℃, drying the fish scales in a freeze dryer for 1-2 days, and treating the fish scales by a crusher to obtain a treated soft fish scale layer;

(3) stirring and mixing the epoxy resin acrylate synthesized in the step (1), 2-hydroxyethyl methacrylate, dipropylene glycol diacrylate and a photoinitiator for 30-50min to obtain a uniform mixed solution; adding the modified inorganic filler and the processed fish scale soft layer into the mixed solution, stirring, and performing ultrasonic treatment for 30-60min to obtain a photo-curable shape memory material precursor mixed solution;

(4) and placing the light-curable shape memory precursor mixed solution in a light-curable 3D printer, exposing the lower layer under a light source with the wavelength of 365-.

6. A preparation method of an enhanced multi-prick laser curing 3D printing shape memory material is characterized by comprising the following steps: the photocuring 3D printer in the step (4) is based on one of stereolithography rapid prototyping, digital light processing prototyping and surface projection micro-stereolithography prototyping technologies.

Technical Field

The invention relates to the field of photocuring 3D printing shape memory materials, in particular to an enhanced multi-prick laser curing 3D printing shape memory material and a preparation method thereof.

Background

3D printing technology, also known as additive manufacturing, is a technology that forms three-dimensional entities by layer-by-layer, layer-by-layer printing, using powdered metal or thermoplastics, based on digital models. The photocuring molding technology is one of 3D printing technologies, photosensitive resin is used as a raw material for 3D printing, internal monomers and prepolymers are polymerized, cured and crosslinked under the condition of light irradiation in the presence of a photoinitiator, and the three-dimensional object is manufactured through layer-by-layer polymerization. At present, the photocuring 3D printing and forming technology comprises stereolithography rapid forming, digital light processing forming, surface projection micro-stereolithography and the like, and is widely applied to industries such as industrial design, aerospace, dentistry, medical treatment, education and the like.

The shape memory polymer is one of functional materials and has wide application prospect. The shape memory material adjusts the state parameters of the shape memory material by responding to the stimulation of external temperature, illumination, humidity, pH value, electromagnetism and the like, and finally restores to the initially set state. Briefly, a material having a particular initial shape that is deformed and fixed to another shape, referred to as the fixed shape, is a temporary shape that returns to the initial shape upon an external physical or chemical stimulus, and is a shape memory polymer. At present, shape memory polymers have been widely used in the fields of biomedicine, packaging materials, intelligent textiles, aerospace and the like.

For example, Chinese patent application No. CN201910191350.3 discloses a preparation method of a 3D printing thermotropic shape memory polylactic acid composite material, and a polycaprolactone modified material is added into a polylactic acid matrix in a physical blending mode to prepare the 3D printing thermotropic shape memory polylactic acid based composite material. The Chinese patent with the application number of CN201710076102.5 discloses a 3D printing shape memory resin material, a preparation method and application thereof, wherein the 3D printing shape memory resin material has the shape memory function under warm water, and the bending rigidity can be adjusted by changing the thickness of a formed film.

Although thermoplastic shape memory polymers have some shape memory function, they have two limitations: firstly, the stimulus source is single, the shape memory process is completed only by thermal stimulation, and the mechanical property is poor; second, the shape memory recovery rate is too slow, by requiring several minutes or even longer to complete the shape memory process. The application prospect of the shape memory polymer is limited to a certain extent.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an enhanced multi-prick laser curing 3D printing shape memory material and a preparation method thereof. The shape memory process can be completed through various stimulations, the shape memory recovery speed is accelerated after the mechanical property is enhanced, the whole shape memory process can be completed only in ten seconds, and the invention is hopeful to be applied to the combination of a photocuring 3D printer:

(1) vascular stents for medical applications;

(2) a passively controlled flexible robot;

(3) domestic intelligence switch.

The invention provides an enhanced multi-prick laser curing 3D printing shape memory material which is prepared from the following raw materials in parts by mass:

epoxy resin acrylate: 20-70 parts of a solvent;

30-60 parts of 2-hydroxyethyl methacrylate;

10-30 parts of dipropylene glycol diacrylate

1-5 parts of a photoinitiator;

0.05-3 parts of modified inorganic filler;

soft layer of the treated fish scales: 1-5 parts.

Preferably, the photoinitiator is at least one of photoinitiator 819, photoinitiator TPO, photoinitiator 184, photoinitiator 784, or photoinitiator ITX.

Preferably, the modified inorganic filler is at least one of carbon black, carbon nanotubes, graphene oxide, MXene or polydopamine, and the modified inorganic filler is subjected to surface modification treatment by a silane coupling agent.

Preferably, the scales of the processed scale soft layer are at least one of grass carp scales, goldfish scales or black carp scales.

A preparation method of an enhanced multi-prick laser curing 3D printing shape memory material comprises the following steps:

(1) synthesis of epoxy resin acrylate: adding 500-600mL butanone solvent into a three-neck flask, adding 50-60 parts by mass of epoxy resin and 15-20 parts by mass of acrylic acid, stirring until the epoxy resin and the acrylic acid are completely dissolved, adding 0.01-0.02 part by mass of triethylamine catalyst and 0.005-0.01 part by mass of 2, 6-di-tert-butyl p-cresol polymerization inhibitor, controlling the reaction temperature to be 90-100 ℃ under the nitrogen protection atmosphere, cooling the temperature to 55-70 ℃ after the reaction is completely finished, discharging, and naturally cooling in the air to obtain the epoxy resin acrylate.

(2) Preparation of the treated soft layer of fish scales: soaking 1-5 parts by mass of fish scales in an acetic acid solution for 2-6min, removing a calcium layer of the fish scales, completely freezing the soaked fish scales at-20 ℃, drying the fish scales in a freeze dryer for 1-2 days, and treating the fish scales by a crusher to obtain a treated soft fish scale layer.

(3) Stirring and mixing the epoxy resin acrylate synthesized in the step (1), 2-hydroxyethyl methacrylate, dipropylene glycol diacrylate and a photoinitiator for 30-50min to obtain a uniform mixed solution; adding the modified inorganic filler and the processed fish scale soft layer into the mixed solution, stirring, and performing ultrasonic treatment for 30-60min to obtain the photo-curable shape memory material precursor mixed solution.

(4) And placing the light-curable shape memory precursor mixed solution in a light-curable 3D printer, exposing the lower layer under a light source with the wavelength of 365-.

Preferably, the photocuring 3D printer in the step (4) is based on one of stereolithography rapid prototyping, digital light processing prototyping and surface projection micro-stereolithography prototyping.

The 3D printed shape memory material can complete the shape memory process through stimulation of heat, light and the like, shows excellent thermotropic and photoinduced deformation recovery functions, is accelerated in shape memory recovery speed after the mechanical property is enhanced, can complete the whole shape memory process only in ten seconds, and has the shape recovery rate of over 90 percent. The preparation method has the advantages of short production period, low cost, time and labor saving and easy industrial production.

Drawings

The invention is further described below with reference to the accompanying drawings.

FIG. 1 is a graph comparing stress-strain curves for a shape memory material reinforced with and without a soft layer of fish scales;

FIG. 2 is a graph comparing the memory speed of shape memory materials enhanced by a soft layer of fish scales and not enhanced by a soft layer of fish scales.

Detailed Description

The present invention is described in detail below by way of examples, which are only used for further illustration of the present invention and are not to be construed as limiting the scope of the present invention, and all other examples obtained by a person of ordinary skill in the art without creative efforts shall fall within the scope of the present invention.