光固化3D直写打印用双酚A型环氧丙烯酸酯光敏树脂的制备和性能研究

doi:10.19491/j.issn.1001-9278.2024.11.005

中国塑料 ›› 2024, Vol. 38 ›› Issue (11): 27-32.DOI: 10.19491/j.issn.1001-9278.2024.11.005

光固化3D直写打印用双酚A型环氧丙烯酸酯光敏树脂的制备和性能研究

房晓彤(), 石烨榕, 胡晶()

北京工商大学轻工科学与工程学院，北京，100048

收稿日期:2024-01-25 出版日期:2024-11-26 发布日期:2024-11-21
通讯作者: 胡晶（1982—），女，副教授，从事生物降解材料及降解机理、金属及其复合材料3D打印成型工艺及机制研究，hujing@th.btbu.edu.cn
E-mail:15753821091@163.com;hujing@th.btbu.edu.cn
作者简介:房晓彤（1998—），女，从事3D打印新材料及成型机制研究，15753821091@163.com

Preparation and performance of bisphenol⁃A type epoxy acrylate photosensitive resin for ultraviolet cured 3D direct ink writing printing

FANG Xiaotong(), SHI Yerong, HU Jing()

School of Light Industry Science and Engineering，Beijing Technology and Business University，Beijing 100048，China

Received:2024-01-25 Online:2024-11-26 Published:2024-11-21
Contact: HU Jing E-mail:15753821091@163.com;hujing@th.btbu.edu.cn

摘要/Abstract

摘要：

以双酚A型环氧丙烯酸酯（EA）为预聚物，1，6⁃己二醇二丙烯酸酯（HDDA）为单体，2，4，6⁃三甲基苯甲酰基二苯基氧化膦（TPO）为引发剂合成了可应用于光固化3D直写打印的自由基型光敏树脂，该树脂可在紫外灯照射下形成交联网络。研究了TPO含量对光敏树脂表干时间、凝胶率和体积收缩率的影响，结果表明，当TPO为6 g时，表干时间最短，凝胶率较高，体积收缩率较大。在此基础上研究了预聚物和单体质量比对光敏树脂表干时间、黏度、凝胶率、体积收缩率和力学性能的影响。结果表明，当 TPO为6 g时，EA 和 HDDA 的质量比为 20/9 时，光敏树脂表干时间最短，黏度较低，凝胶率最大，力学性能较为优异，适合光固化3D直写打印。

关键词: 光敏树脂, 3D直写打印, 双酚A型环氧丙烯酸酯, 1，6?己二醇二丙烯酸酯, 2，4，6?三甲基苯甲酰基二苯基氧化膦

Abstract:

A free radical photosensitive resin suitable for ultraviolet （UV） cured 3D direct ink writing printing was synthesized using bisphenol⁃A epoxy acrylate （EA） as a prepolymer， 1，6⁃hexanediol diacrylate （HDDA） as a monomer， and 2，4，6⁃trimethylbenzoyl diphenylphosphine oxide （TPO） as an initiator. The resin could form a cross⁃linked network under UV irradiation. The effect of TPO content on the surface drying time， gel rate， and volume shrinkage of photosensitive resin were investigated. The results indicated that when 6 g TPO was added， the surface drying time of the cured resin was the shortest， its gel rate was highest， and its volume shrinkage was largest. According to these results， the effect of the mass ratio of prepolymer to monomer on the surface drying time， viscosity， gel rate， volume shrinkage， and mechanical properties of the photosensitive resin were investigated. The results demonstrated that the photosensitive resin containing 6 g TPO had the shortest surface drying time， lower viscosity， the largest gel rate， and excellent mechanical properties at an EA/HDDA of 20/9. This suggests that the developed photosensitive resin is suitable for use in UV cured 3D direct ink writing printing.

Key words: photosensitive resin, 3D direct ink writing printing, bisphenol A epoxy acrylate, 1，6?hexanediol diacrylate, 2，4，6?trimethylbenzoyl diphenylphosphine oxide

中图分类号:

TQ322

房晓彤, 石烨榕, 胡晶. 光固化3D直写打印用双酚A型环氧丙烯酸酯光敏树脂的制备和性能研究[J]. 中国塑料, 2024, 38(11): 27-32.

FANG Xiaotong, SHI Yerong, HU Jing. Preparation and performance of bisphenol⁃A type epoxy acrylate photosensitive resin for ultraviolet cured 3D direct ink writing printing[J]. China Plastics, 2024, 38(11): 27-32.

图/表 13

样品编号	EA	HDDA	TPO
1	100	45	4
2	100	45	5
3	100	45	6
4	100	45	7
5	100	45	8

表1 用于研究光引发剂含量对树脂性能影响的样品配方 (g)

Tab.1 Formula of the samples used to study the effect of photoinitiator content on resin properties

样品编号	EA/g	HDDA/g	TPO/g	EA/HDDA质量比
1	100	20	6	20/4
2	100	25	6	20/5
3	100	30	6	20/6
4	100	35	6	20/7
5	100	40	6	20/8
6	100	45	6	20/9

表2 用于研究预聚物和单体质量比对树脂性能影响的样品配方

Tab.2 Formula of the samples used to study the effect of prepolymer and monomer mass ratio on resin properties

图1 TPO吸收紫外光产生活性自由基的原理

Fig.1 Mechanism of TPO absorbing ultraviolet light to produce reactive free radicals

图2 EA/HDDA/TPO光固化反应机理

Fig.2 Mechanism of the EA/HDDA/TPO photopolymerization reaction

图3 光敏树脂固化前后的FTIR谱图

Fig.3 FTIR spectra of photosensitive resin before and after light curing

图4 HDDA和光敏树脂的1H⁃NMR谱图

Fig.4 1H⁃NMR spectra of the HDDA and photosensitive resin

图5 TPO含量对表干时间的影响

Fig.5 Effect of TPO content on surface drying time

图6 TPO含量对凝胶率和体积收缩率的影响

Fig.6 Effect of TPO content on gel rate and volume shrinkage

图7 EA和HDDA质量比对黏度的影响

Fig.7 Effect of mass ratio of EA and HDDA on viscosity

图8 EA和HDDA质量比对表干时间的影响

Fig.8 Effect of mass ratio of EA and HDDA on surface drying time

图9 EA和HDDA质量比对凝胶率和体积收缩率的影响

Fig.9 Effect of mass ratio of EA and HDDA on gel rate and volume shrinkage

图10 EA和HDDA质量比对力学性能的影响

Fig.10 Effect of mass ratio of EA and HDDA on mechanical properties

图11 光固化3D直写装置及打印样品

Fig.11 UV curing 3D direct ink writing device and the printing sample

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光固化3D直写打印用双酚A型环氧丙烯酸酯光敏树脂的制备和性能研究

Preparation and performance of bisphenol⁃A type epoxy acrylate photosensitive resin for ultraviolet cured 3D direct ink writing printing

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