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Photo-thermal double curing 3D printing method and product thereof

A 3D printing and dual curing technology, applied in the field of 3D printing, can solve the problems of easy brittleness and loss of toughness of products, achieve good toughness, improve elongation at break, and broaden the scope of application.

Active Publication Date: 2019-08-16
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] It can be seen that if the epoxy resin thermal curing system is used as the dark curing system in the light-dark dual curing system in 3D printing, the thermal curing temperature of the epoxy resin will generally be higher than that of the first-stage light-curing polymer glass. temperature (the glass transition temperature of this product is higher than room temperature), so the light-cured polymerization product becomes brittle after returning to room temperature, resulting in epoxy resin light-dark dual-cure products are easy to become brittle and lose basic toughness

Method used

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  • Photo-thermal double curing 3D printing method and product thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0025] (1) Preparation of polyurethane polyacrylate: mix 1mol PPG-1000 with DBT accounting for 0.5% by weight of PPG-1000, add dropwise to 2mol HDI, react at 60°C for 1h, then add 2mol HEA, react at 60°C for 3h, Obtain polyether urethane acrylate;

[0026] (2) Light-thermal dual curing 3D printing: mix the polyether urethane acrylate obtained in step (1) with HDDA and TPO according to the following mass percentages, and use a light-curing printer for 3D printing to obtain a photopolymer. Test The glass transition temperature of the photopolymer is -18°C, which is lower than room temperature; then according to the following mass percentage, mix polyether urethane acrylate, HDDA, TPO, dicyandiamide curing agent and bisphenol A epoxy resin and then photocure and print , and then heated to 160 ° C for 6 hours to obtain 3D printed products; the dicyandiamide curing agent is produced by Guangzhou Xinxi Metallurgical Chemical Co., Ltd., the brand name is SH-300, and the bisphenol A e...

Embodiment 2

[0029] (1) Preparation of polyurethane polyacrylate: mix 1mol PCDL-1000 with DBT accounting for 0.5% by weight of PCDL-1000, add dropwise to 2mol HDI, react at 60°C for 1h, then add 2mol HEA, react at 60°C for 3h, Obtain polyester urethane acrylate;

[0030] (2) Photo-thermal dual curing 3D printing: mix the polyester urethane acrylate obtained in step (1) with HDDA and TPO according to the following mass percentage, and use a light-curing printer to perform 3D printing to obtain a polymer, and test the polymer. The glass transition temperature is -11°C, which is lower than room temperature; according to the following mass percentage, mix polyester urethane acrylate, HDDA, TPO, imidazole curing agent and polyurethane modified epoxy resin evenly, light-cure and print, and heat to After curing at 110°C for 6 hours, the 3D printed product was obtained; the imidazole curing agent was produced by Guangzhou Xinxi Metallurgical Chemical Co., Ltd., the brand name is SH-A80, and the po...

Embodiment 3

[0033] (1) Preparation of polyurethane polyacrylate: mix 1mol PCDL-1000 with DBT accounting for 0.5% by weight of PCDL-1000, add dropwise to 2mol HDI, react at 60°C for 1h, then add 2mol HEA, react at 60°C for 3h, Obtain polyester urethane acrylate;

[0034](2) Photo-thermal dual curing 3D printing: the polyester urethane acrylate obtained in step (1) is mixed with IBOA and TPO according to the following mass percentage, and 3D printing is performed using a light-curing printer to obtain a polymer, and the polymer is tested. The glass transition temperature is 6°C, which is lower than room temperature; according to the following mass percentage, mix polyester urethane acrylate, IBOA, TPO, ammonium blocked Lewis acid salt and alicyclic epoxy resin evenly, light-cure 3D printing, and then heat After curing at 100°C for 6 hours, 3D printed products were obtained; the ammonium-blocked Lewis acid salt was purchased from Shenzhen Kaiji Applied Materials Co., Ltd., trade name Vicbase...

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Abstract

The invention discloses a photo-thermal double curing 3D printing method and a product thereof, and the photo-thermal double curing 3D printing method comprises the following steps: mixing raw materials, carrying out photocuring 3D printing, and heating and curing to obtain a 3D printed product. The raw materials include polyurethane acrylate, a diluent, an initiator, epoxy resin and a thermotropic curing agent. The polyurethane acrylate is obtained by reacting isocyanate with polyol and then capping with hydroxyl-containing acrylate, and the polyol is polyester polyol or polyether polyol withthe molecular weight not less than 1000. The method avoids the phenomenon that polymerization products become brittle due to thermal curing of epoxy resin, realizes the basic toughness of epoxy resindual curing products, and meets the application in industrial manufacturing.

Description

technical field [0001] The invention relates to the field of 3D printing, in particular to a method of photothermal dual curing 3D printing and a product thereof. Background technique [0002] Light-curing 3D printing products are thermosetting resins. Thermosetting materials are a type of cross-linked polymer materials with a network structure. The biggest weakness of the cross-network structure of thermosetting resins is that they are brittle after curing and have poor impact and stress crack resistance. , the plastic deformation is constrained, which limits their application in some fields. In addition, due to the limitation of photocuring printing technology, photosensitive resins with small molecular weight and low viscosity are generally used, and the polymerization degree of photosensitive resin monomers is not high during the printing process, so the mechanical properties of the obtained 3D printed products are insufficient. The introduction of light-dark dual-curin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L51/08C08L63/00C08F283/00C08F220/18C08F222/14C08G18/67C08G18/48C08G18/44B33Y70/00
CPCB33Y70/00C08F283/008C08G18/44C08G18/4825C08G18/672C08L51/08C08L63/00C08G18/48C08F220/1811
Inventor 陈遒刘丹丹来国桥胡自强
Owner HANGZHOU NORMAL UNIVERSITY
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