自互补多元氢键添加剂可增强3D打印的PMMA结构的热机械性能,Macromolecules

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自互补多元氢键添加剂可增强3D打印的PMMA结构的热机械性能
Macromolecules ( IF 5.1 ) Pub Date : 2019-07-17 00:00:00 , DOI: 10.1021/acs.macromol.9b00546
Dayton P. Street , William K. Ledford , Abigail A. Allison ₁ , Steven Patterson ₂ , Deanna L. Pickel ₃ , Bradley S. Lokitz ₄ , Jamie M. Messman ₂ , S. Michael Kilbey

Affiliation

非键相互作用提供了一种引导组装并改变软聚合物材料的物理性能的方法。在这里，通过聚合物添加剂传递的自互补氢键相互作用显着增强了通过熔融长丝制造（FFF）印刷的聚甲基丙烯酸甲酯（PMMA）标本的热机械性能。由甲基丙烯酸甲酯（MMA）和含有2-脲基-4-嘧啶酮（UPy）侧基（UPyMA）的甲基丙烯酸酯单体组成的无规共聚物添加剂，通过四重氢键相互作用自聚，并以1 wt％的比例加入。高分子量PMMA基质。在玻璃态下进行的动态力学分析测量结果表明，p（MMA- r-UPyMA）共聚物添加剂最多增加5 mol％，杨氏模量增加50％，储能模量增加62％。同时，极限抗拉强度增加了85％，抗拉模量增加了100％。另外，流变学测量表明，在远高于玻璃化转变温度的温度下，多组分共混物的储能模量和复数粘度不受p（MMA- r- UPyMA）添加剂掺入的影响，而与UPyMA的含量无关。总的来说，这些结果表明，使用可逆的，非键合的分子间相互作用，例如多齿氢键键合，提供了一种新颖的途径，可以克服FFF印刷材料的机械性能局限性，而不会影响熔融加工性。

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Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures

Nonbonded interactions provide a way to guide the assembly and alter the physical properties of soft polymeric materials. Here, self-complementary hydrogen-bonding interactions conveyed through polymeric additives dramatically enhance thermomechanical properties of poly(methyl methacrylate) (PMMA) specimens printed by fused filament fabrication (FFF). Random copolymer additives composed of methyl methacrylate (MMA) and a methacrylate monomer containing 2-ureido-4-pyrimidone (UPy) pendant group (UPyMA), which self-dimerize through quadruple hydrogen-bonding interactions, were incorporated at 1 wt % in a high molecular weight PMMA matrix. Results from dynamic mechanical analysis measurements made in the glassy regime show that as the UPyMA comonomer content in the p(MMA-r-UPyMA) copolymer additive increases up to 5 mol %, there is a 50% increase in Young’s modulus and a 62% increase in the storage modulus. Concomitantly, there is an 85% increase in ultimate tensile strength and a 100% increase in tensile modulus. Additionally, rheology measurements indicate that at temperatures well above the glass transition temperature, the storage modulus and complex viscosity of the multicomponent blends are unaffected by the incorporation of p(MMA-r-UPyMA) additives, regardless of the UPyMA content. In aggregate, these results suggest that using reversible, nonbonded intermolecular interactions, such as multidentate hydrogen bonding, provides a novel route to overcome the mechanical property limitations of FFF-printed materials without affecting melt processability.

更新日期：2019-07-17

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