嵌段共聚物/均聚物共混体系中动力学构筑具有类似石墨烯堆砌方式的柱状有序结构的理论模拟OA
Kinetic Fabrication of Ordered Mesostructures with Graphene-Like Packing of Cylindrical Domains in Block Copolymer/Homopolymer Blends by Theory and Simulations
嵌段共聚物是一种通过强有力的共价键将2种或者多种在化学上互不相同和在热力学上互不相容的均聚物相互连接在一起而形成的特殊高分子.受益于这些共价键的限制作用,嵌段共聚物能够通过不同嵌段之间的聚集和分离自发地自组装形成种类十分丰富的纳米有序结构,受到了许多前沿科学领域研究人员的广泛关注,尤其是其中具有类似石墨烯堆砌方式的柱状有序结构,由于其是一种十分优异的二维光子晶体,一直备受关注.在之前的研究中,虽然通过采用调节嵌段共聚物的链拓扑结构等热力学构筑方法可以获取具有类似石墨烯堆砌方式的柱状有序结构的稳定相区,但是所需要的链拓扑结构却十分复杂,而通过调控嵌段共聚物的非平衡态形貌演化动态过程进行动力学构筑虽然能够显著降低链拓扑结构的复杂程度,但是相关研究迄今为止尚未涉及共混这一因素的影响,也就是说,对于在嵌段共聚物体系中构筑具有类似石墨烯堆砌方式的柱状有序结构的相关研究来说,寻找出更为行之有效的构筑方法依然是目前研究的重点之一.鉴于此,在本研究中,通过将快速化学成分转变线形ACB三嵌段共聚物与线形均聚物A进行共混,设计了快速化学成分转变线形ACB三嵌段共聚物/线形均聚物A这一共混体系,利用C嵌段组分由B组分到A组分的快速转变,并且基于热力学稳定的六角堆积柱状有序结构构建起始演化结构,采用高分子场论和谱方法的数值求解技术,研究了线形均聚物A的加入对起始于这些起始演化结构的、最后能够抵达具有类似石墨烯堆砌方式的柱状有序结构的非平衡态形貌演化动态过程的影响.通过研究发现,线形均聚物A在共混体系中的含量越多,最后能够抵达具有类似石墨烯堆砌方式的柱状有序结构的非平衡态形貌演化动态过程,在构建相应的起始演化结构时所需要的C嵌段长度越短,越有利于具有类似石墨烯堆砌方式的柱状有序结构的动力学构筑.
Block copolymer is a special type of polymers and is formed by connecting two or more chemically distinct and thermodynamically incompatible homopolymers together via strong covalent bonds.Benefiting from the constraints of these covalent bonds,block copolymers can spontaneously self-assemble into a variety of ordered mesostructures at the length scale of nanometers through the aggregation and separation of different blocks,which attracts extensive attention from the researchers in many advanced scientific fields.In particular,the ordered mesostructure with graphene-like packing of cylindrical domains is very attractive because it is an exceptionally excellent two-dimensional photonic crystal.While the stable regions of the ordered mesostructure with graphene-like packing of cylindrical domains can be obtained via the thermodynamical fabrication strategies,e.g.,fine-tuning chain architecture of block copolymers,the chain required architectures are very complex.Whereas the kinetic fabrication strategy by adjusting the nonequilibrium kinetic processes of morphological evolution of block copolymers can significantly reduce the complexity of used chain architectures,the related researches so far has not considered the effect from the blending.In other words,for the researches that focus on the fabrication of the ordered mesostructure with graphene-like packing of cylindrical domains in block copolymers,seeking more effective fabrication strategies remains a key research focus.In this study,based on the thermodynamically stable hexagonally packed cylinders(hex),by designing the blends of linear ACB triblock copolymers and linear A homopolymers,where the chemophysical properties of C-blocks can be rapidly altered from B to A,to generate starting states,we explore the nonequilibrium kinetic processes of morphological evolution ensuing from these starting states as well as the effect from the addition of linear A homopolymers by the polymer field theory and the spectral method.Our obtained results illustrate that the more the addition of linear A homopolymers,the shorter the length of C-block that is required when generating the unstable state,ensuing from which the nonequilibrium kinetic processes of morphological evolution can finally reach the ordered mesostructure with graphene-like packing of cylindrical domains,benefitting the kinetic fabrication of the ordered mesostructure with graphene-like packing of cylindrical domains.
孙浩原;孙德文
中国科学技术大学应用化学与工程学院,合肥 230026||中国科学院长春应用化学研究所,高分子科学与技术全国重点实验室,长春 130022中国科学技术大学应用化学与工程学院,合肥 230026||中国科学院长春应用化学研究所,高分子科学与技术全国重点实验室,长春 130022
化学化工
嵌段共聚物柱状有序结构共混非平衡态形貌演化动态过程快速化学成分转变
Block copolymerCylindrical mesostructureBlendNonequilibrium kinetic processes of morphological evolutionRapid-chemical-component transformation
《应用化学》 2026 (6)
887-896,10
吉林省自然科学基金(No.20240101173JC)和国家自然科学基金(Nos.21973090,22373029)资助 Supported by the Science and Technology Development Program of Jilin Province(No.20240101173JC)and the National Natural Science Foundation of China(Nos.21973090,22373029)
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