Mechanically Robust and Reprocessable Acrylate Vitrimers with Hydrogen-Bond-Integrated Networks for Photo-3D Printing,ACS Applied Materials & Interfaces

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Mechanically Robust and Reprocessable Acrylate Vitrimers with Hydrogen-Bond-Integrated Networks for Photo-3D Printing
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2020-12-23 , DOI: 10.1021/acsami.0c19520
Hong Gao ₁ , Yingchun Sun ₁ , Miaomiao Wang ₁ , Zhen Wang ₁ , Guoqiang Han ₁ , Ling Jin ₁ , Peng Lin ₁ , Youyi Xia ₁ , Kui Zhang ₁

Affiliation

Reprocessable acrylate vitrimer needs to enhance its strength to expand the application in photo-three-dimensional (photo-3D) printing. However, the methods for improving mechanical properties by the addition of nanofillers or a multifunctional resin into acrylate vitrimers are inappropriate for photo-3D printing due to the low curing speed of photopolymerization induced by weakening light transmittance or reduction of dimensional accuracy caused by large shrinkage. At present, we demonstrate a new strategy for developing a kind of mechanically robust and reprocessable 3D printing thermosets by combining hydrogen bonds and exchangeable β-hydroxyl esters into acrylate vitrimers. To realize this purpose, diacrylate prepolymer containing β-hydroxyl esters was first synthesized from glycidyl methacrylate and suberic acid. Then, the resin formulations for 3D printing comprising the synthesized diacrylate prepolymer together with acrylamide generate exchanged β-hydroxyl ester and pendent amide in cross-linked networks. Here, hydrogen bonds resulting from the amide group as sacrificial bonds dissipate vast mechanical energy under an external load. With the inclusion of 20 wt % acrylamide, the average tensile strength and Young’s modulus are up to 40.1 and 871 MPa, which increased by about 4.4 and 3.85 times, respectively. The network rearrangement of cross-linked vitrimers can be achieved through the dynamic ester exchange reactions with gradual disappearance of hydrogen bonds at elevated temperatures, imparting reprocessability into the printed structures. Various photo-3D printing or UV irradiation shapes were successfully produced, and these dissolved in ethylene glycol could be remolded again.

中文翻译：

具有氢键集成网络的机械坚固且可再加工的丙烯酸盐微晶玻璃，用于Photo-3D打印

可再加工的丙烯酸酯微晶玻璃需要增强其强度，以扩大在光三维（photo-3D）打印中的应用。然而，通过将纳米填料或多功能树脂添加到丙烯酸酯微晶聚合物中来改善机械性能的方法不适合于光3D打印，这是由于由弱的透光率引起的光聚合的固化速度低或由大的收缩引起的尺寸精度的降低。目前，我们展示了一种通过将氢键和可交换的β-羟基酯结合到丙烯酸酯三聚体中来开发一种机械性能强且可再加工的3D打印热固性塑料的新策略。为了实现该目的，首先由甲基丙烯酸缩水甘油酯和辛二酸合成含有β-羟基酯的二丙烯酸酯预聚物。然后，包含合成的二丙烯酸酯预聚物和丙烯酰胺的3D打印树脂配方会在交联网络中生成交换的β-羟基酯和侧酰胺。在此，由酰胺基产生的氢键作为牺牲键在外部负载下耗散了巨大的机械能。加入20wt％的丙烯酰胺，平均抗拉强度和杨氏模量分别高达40.1和871MPa，分别增加了约4.4和3.85倍。交联的三聚体的网络重排可通过动态酯交换反应实现，在高温下氢键逐渐消失，从而赋予印刷结构以可再加工性。各种照片3D打印或UV辐射形状已成功生产，

更新日期：2021-01-13

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