【作者】 王涛；

【导师】 林润雄；

【作者基本信息】 青岛科技大学 ， 材料加工工程， 2019， 硕士

【摘要】 三维(3D)打印是通过逐层连续叠加来制作3D对象的过程。在各种3D打印方法中,光化学聚合方法非常有吸引力,因为形状复杂的物体可以通过光敏树脂材料的光聚合反应直接产生,具有低成本、易生产、无污染的特点。制造高精度3D打印机器和制备高性能光敏树脂材料,是发展光化学法3D打印的两个重要方面。目前国内外3D打印机器已经发展成熟,但是光敏树脂材料发展缓慢,特别是在国内,至今依然很少有自主生产的高性能光敏树脂材料。本论文包括以下内容。论文首先介绍了3D打印机和光敏树脂材料的研究现状,并着重分析了光敏树脂材料的发展和不足之处。分析表明,透明性好并不发黄的光敏树脂材料,是目前最欠缺也是最重要的基础材料。因此,开发一种透明并且不发黄的光敏树脂材料,具有重要意义。研究不同种类的光引发剂、稀释剂和低聚物对光敏树脂性能的影响,发现不论是能产生生色基团的含苯环树脂体系,还是有抗黄变性能的脂肪族树脂体系,都没有完全透明且不发黄的光敏树脂,并且力学性能随稀释剂的添加而降低。这是由于低聚物粘度太大,需要加入大量的小分子稀释剂,导致了3D打印样件精度、力学性能、透明度的下降,以及材料黄变的产生。所以本研究考虑是否可以采用无低聚物或者少低聚物体系,用粘度适当的刚性单体代替低聚物,减少稀释剂用量,减少材料中小分子比例,制作出力学性能较好、透明且无黄变的光敏树脂材料。通过两步法合成了一种带有反应性基团的刚性单体:二乙氧化双酚A双甲基丙烯酸酯(2EO-BPADMA)。将2EO-BPADMA与稀释剂HEMA和TPGDA、引发剂TPO和BDK,配制光敏树脂。通过对不同树脂材料的固化深度、凝胶含量、粘度、收缩率和固化后试样基本力学性能的比较,确定了一种综合性能最优的光敏树脂配方。然后再加入SiO2、JZ-303和JZ-305进行改性,可以提高材料力学性能。通过改性,虽然力学性能上已经很接近德国一种透明性较好的Foto Tec DLP.A型光敏树脂,但是材料仍有微黄存在。光敏树脂黄变的主要原因是体系中存在小分子,而小分子又是光敏树脂不可缺少的成分。为了解决黄变,先通过实验找出了材料黄变的主要诱导因素是光照,再使用光稳定剂622、光稳定剂292、二氧化钛和无机群青彻底解决了光敏树脂材料固化变黄问题,制备出了一种3D打印用透明且无黄变的光敏树脂,并做了一些拓展研究。更多还原

【Abstract】 Three-dimensional(3D)printing is a process of making 3D objects by successively superimposing layer by layer.Among various 3D printing methods,photochemical polymerization methods are very attractive because objects with complicated shapes can be directly produced by photopolymerization of photosensitive resin materials,which has the characteristics of low cost,easy production and no pollution.The manufacture of high-precision 3D printers and the preparation of high-performance photosensitive resin materials are two important aspects in the development of photochemical 3D printing.At present,3D printers at home and abroad have matured,but the development of photosensitive resin materials is slow,especially in China,and there are still few high-performance photosensitive resin materials produced by ourselves.This paper includes the following.The paper first introduces the research status of 3D printers and photosensitive resin materials,and focuses on the development and inadequacies of photosensitive resin materials.The analysis shows that the photosensitive resin material with good transparency and not yellowing is the most lacking and most important basic material at present.Therefore,it is of great significance to develop a photosensitive resin material which is transparent and does not yellow.The effects of different types of photoinitiators,diluents and oligomers on the properties of bright resins were investigated.It was found that no matter whether it is a benzene ring-containing resin system capable of producing a chromophore group or an aliphatic resin system having anti-yellowing properties,there is nophotosensitive resin which is completely transparent and does not yellow,and the mechanical properties are added with the diluent.And lower.This is due to the fact that the viscosity of the oligomer is too large,and a large amount of small molecule diluent needs to be added,resulting in a decrease in the accuracy,mechanical properties,transparency of the 3D printed sample,and yellowing of the material.Therefore,this study considers whether it is possible to use oligomer-free or oligomer-free systems to produce photosensitive resin material with better mechanical properties,transparency and without yellowing by using rigid monomers to replace oligomers with appropriate viscosity,reducing the amount of diluent,reducing the proportion of small molecules in the material.A rigid monomer with a reactive group was synthesized by a two-step process:2-Ethoxybisphenol A Dimethacrylate(2EO-BPADMA).Photosensitive resins with different properties were prepared by comparing 2EO-BPADMA with diluents HEMA and TPGDA,initiators TPO and BDK.Through comparison of curing depth,gel content,viscosity,shrinkage rate and basic mechanical properties of cured samples of different resin materials,a photosensitive resin formula with optimal comprehensive properties was determined.Then add SiO2,JZ-303 and JZ-305 for modification,which can improve the mechanical properties of the material.Through modification,although the mechanical properties are very close to a kind of photosensitive resin of Foto Tec DLP.A type which is better in transparency,the material still has yellowish color.The main reason for the yellowing of photosensitive resin is the presence of small molecules in the system,which are indispensable components of photosensitive resins.In order to solve the yellowing,the main inducing factor of the yellowing of the material was light by the conditional experiment.Then the light stabilizer 622,the light stabilizer 292,the titanium dioxide and the inorganic ultramarine blue were used to completely solve the problem of curing yellowing of the photosensitive resin material.A transparent and non-yellowing photosensitive resin for 3D printing was produced and some research was done.更多还原