【作者】 张建成；

【导师】 周政；

【作者基本信息】 北京化工大学 ， 材料科学与工程， 2019， 硕士

【摘要】 紫外光固化三维打印材料通常使用液态光敏树脂作为原材料,在特定波长紫外激光束照射下进行逐层快速固化的一种工艺。由于具有低能耗、无溶剂、反应条件温和、成型精度高、固化速率快等特性,近年来受到人们更多的关注。然而传统的自由基光固化树脂成型速度慢、收缩率高、力学性能较差,为了解决这些问题,我们通过添加阳离子组分、硫醇单体组分对基体树脂进行改进,并引入了具有有机-无机杂化结构的多官能度笼型倍半硅氧烷(POSS),对紫外光固化树脂体系进行进一步的性能改进。主要工作概述如下:1、成功制备了甲基丙烯酰氧丙基笼型倍半硅氧烷(MAP-POSS)、甲基丙烯酰氧丙基/2-(3,4-环氧环己基)乙基多官能团笼型倍半硅氧烷(ME-POSS),并通过FTIR、1H-NMR、29Si-NMR、MS、GPC 等表征,证实制备成功;2、使用MAP-POSS、ME-POSS分别改性自由基型、自由基-阳离子混杂型紫外光固化树脂体系,通过实时转化率、体积收缩率、SEM、拉伸性能、硬度、DMA、TGA等一系列性能测试,结果表明两种改性单体MAP-POSS、ME-POSS改性后的紫外光固化树脂具有更高的力学性能和热稳定性能,ME-POSS改性材料具有降低固化收缩率的作用。3、使用MAP-POSS作为树脂基体制备巯基烯型紫外光固化树脂体系。使用不同含量硫醇单体三羟甲基丙烷三(3-巯基丙酸)酯(TTMP)、季戊四醇四(3-巯基丙酸)酯(PETMP)分别对甲基丙烯酰氧丙基笼型倍半硅氧烷/三乙二醇二甲基丙烯酸酯(MAP-POSS/TEGDMA)体系进行性能改性,同时也进行了实时转化率、XRD、SEM-EDAX、体积收缩率、拉伸性能、硬度、DMA、TGA等一系列性能测试,结果表明以MAP-POSS为树脂基体所制备的材料具有更高的力学性能和热稳定性,同时巯基的引入能够明显增加材料的实时转化率。更多还原

【Abstract】 The UV-cured three-dimensional printing material is a process of rapidly curing layer by layer under irradiation of a specific wavelength ultraviolet laser beam,which uses a liquid photosensitive resin as a raw material.Due to its low energy consumption,solvent-free,mild reaction conditions,high molding accuracy,and fast curing rate,it has received more attention in recent years.However,the conventional radical photocurable resin has a slow molding speed,a high shrinkage rate,and a poor mechanical property.To solve this phenomenon,the photocurable resin could be improved by adding a cationic component and a thiol monomer component.At the same time,we added a multi-functional polyhedral silsesquioxane(POSS)with an organic-inorganic hybrid structure to further improve the performance of the photocured three-dimensional printing resin system.The main work is summarized as follows:1.MAP-POSS and ME-POSS were successfully prepared,and confirmed by FTIR,1H-NMR,29Si-NMR,MS and GPC.2.MAP-POSS and ME-POSS were used to improve the performance of free radical and free radical-cationic UV-curing resin systems.A series of performance tests such as real-time conversion rate,volume shrinkage,SEM,tensile properties,hardness,DMA,TGA,etc.were performed.Studies had shown that the two modified monomers MAP-POSS and ME-POSS were beneficial to the performance improvement of UV-curing resin.Among them,MAP-POSS modified free radical UV-curing three-dimensional printing resin had higher mechanical properties and thermal stability.ME-POSS could improve the mechanical properties and thermal stability of free radical-cationic UV-curing resins,and reduce the volume shrinkage.3.A thiol-ene type UV-curing resin system was prepared using MAP-POSS as a resin matrix.We modified the MAP-POSS/TEGDMA system with different amounts of TTMP and PETMP thiol monomers.At the same time,real-time conversion rate,XRD,SEM-EDAX,volume shrinkage,tensile properties,hardness,DMA,TGA and other performance tests were also carried out.The results showed that the materials prepared by MAP-POSS as the matrix resin had higher mechanical properties and thermal stability.At the same time,the introduction of mercaptan could significantly increase the real-time conversion rate of the material.更多还原