Controlling Morphology of Polymer Particles Synthesized from Condensed Monomer Droplets

Controlling Morphology of Polymer Particles Synthesized from Condensed Monomer Droplets
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控制由凝聚的单体液滴合成的聚合物颗粒的形态

DOI:
10.1021/acs.chemmater.3c00285
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发表时间:
2023
影响因子:
8.6
通讯作者:
Yang, Rong
Yang, Rong
中科院分区:
材料科学2区
文献类型:
--
作者:
Franklin, Trevor;Yang, Rong

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具有可调形态的非球形聚合物纳米颗粒是一类新兴的功能材料,在药物输送、传感和软机器人方面具有巨大的潜力。然而,它们的发展目前受到费力的合成和对颗粒形态的有限控制的限制。为了弥合这一差距,我们证明了一个简单的合成技术,即冷凝液滴聚合(CDP),在气相沉积装置中获得不同形态的非球形颗粒的能力。形态控制通过独特的原位数字显微镜实现,其揭示了当未反应的单体通过蒸发从部分聚合的液滴中除去时颗粒形态发展的真实的演变。以甲基丙烯酸苄酯(BzMA,lowkp和lowTg)和丙烯酸(AA,highkp和highTg)为例,研究了单体增长常数(kp)和聚合物玻璃化转变温度(Tg)等基本性质对粒子形态的影响,以指导粒子形态的设计。部分聚合的BzMA液滴在单体蒸发过程中各向同性收缩,产生紧凑的聚合物圆顶,而部分聚合导致聚合层包含未反应的AA单体,其在单体去除后变成褶皱的聚合物壳或粒状颗粒。这样的洞察力提供了一个框架,了解粒子形态形成的基本机制。工艺-性能相关性有助于提高CDP中聚合物形态的控制,其有用的应用范围从药物递送到软机器人。
Non-spherical polymer nanoparticles with tunable morphology are an emerging class of functional materials with enormous potential in drug delivery, sensing, and soft robotics. However, their development is currently limited by the laborious synthesis with limited control over particle morphology. To bridge that gap, we demonstrate the capability of a facile synthesis technique, namely, condensed droplet polymerization (CDP), to obtain non-spherical particles with disparate morphologies in a vapor deposition apparatus. The morphological control is enabled by a unique in situ digital microscopy, which reveals the evolution of particle morphology development in real time as the unreacted monomer was removed from the partially polymerized droplets through evaporation. To guide particle morphology design, the effect of fundamental properties, such as the monomer propagation constant (kp) and polymer glass transition temperature (Tg), on the resulting particle morphology was investigated using benzyl methacrylate (BzMA, lowkpand lowTg) and acrylic acid (AA, highkpand highTg) as examples. Partially polymerized BzMA droplets shrank isotropically during monomer evaporation, giving rise to compact polymer domes, whereas partial polymerization led to a polymerized layer encompassing unreacted AA monomer, which became wrinkled polymer shells or granular particles upon monomer removal. Such insight provides a framework for understanding the fundamental mechanisms of particle morphology formation. The process–property correlations serve to advance the control over polymer morphology in CDP with useful applications ranging from drug delivery to soft robotics.
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