Revealing the Influences of Solvent Boiling Point and Alkyl Chains on the Adlayer Crystallinity of Furan-Diketopyrrolopyrrole-Thienylene Copolymer at Molecular Level.
Revealing the Influences of Solvent Boiling Point and Alkyl Chains on the Adlayer Crystallinity of Furan-Diketopyrrolopyrrole-Thienylene Copolymer at Molecular Level.
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DOI：
10.1021/acs.langmuir.9b02604
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发表时间：
2019-12
期刊：
影响因子：
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通讯作者：
Jin-Kuo Li;Ming-Yue Shao;Miao Yu;Weifeng Zhang;Zhi-Yong Yang;G. Yu;Jingcheng Xu;W. Cui
中科院分区：
文献类型：
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作者：
Jin-Kuo Li;Ming-Yue Shao;Miao Yu;Weifeng Zhang;Zhi-Yong Yang;G. Yu;Jingcheng Xu;W. Cui
聚合物的表面结晶度由低沸点（L-bp）浇铸的（3，6-二呋喃-2-基-2，5-二（2-辛基十二烷基）-吡咯并[3，4-c]吡咯-1，4-二酮-噻吩亚乙烯基（PDVF）吸附层，通过扫描隧道显微镜（STM）研究了中bp（M-bp）和高bp（H-bp）溶剂，并在汉森溶解度参数（HSP）理论和分子动力学（MD）模拟。从L-到H-bp溶剂，PDVF吸附层的结晶度明显增加，并且当溶剂bp位于同一基团时，含烷基链的溶剂如EB（EB）比不含烷基链的溶剂如CB（CB）更有利于结晶度的提高。HSP空间公开了与CB相比，EB是PDVF的边缘溶剂。分子动力学模拟结果表明，准孤立的PDVF在EB溶液中通过表面组装机制促进了晶化畴的形成。而在CB中，通过分子间重叠而互连的PDVF分子倾向于通过在溶液中直接沉积预形成的结构而产生无定形结构。
Surface crystallinity of the polymer poly(3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-altthieylenevinylene (PDVF) adlayers casted from low- boiling point (L-bp), medium-bp (M-bp) and high-bp (H-bp) solvents were investigated through scanning tunneling microscopy (STM) and analyzed in the assistance of Hansen solubility parameter (HSP) theory and molecular dynamics (MD) simulations. Crystallinity of PDVF adlayers increase evidently from the L- to H-bp solvent and the solvent with alkyl chain such as ethylbenzene (EB) facilitates improving crystallinity also than the one without alkyl chain such as chlorobenzene (CB) if the solvent bp locates in the same group. HSP space discloses that EB is a marginal solvent for PDVF in contrast to CB. Quasi-isolate PDVF in EB solution revealed by MD simulations facilitates forming crystallized domains through surface assembling mechanism. Whereas in CB, interconnected PDVF molecules through intermolecular overlapping tend to generate amorphous structures through direct deposition of pre-formed structures in solution.