Synthesis and Characterization of Cationic Dendrimer-PDMS Hybrids.

Synthesis and Characterization of Cationic Dendrimer-PDMS Hybrids.
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DOI:
10.1002/marc.202000652
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发表时间:
2021-04
影响因子:
4.6
通讯作者:
Gutekunst WR
Gutekunst WR
中科院分区:
化学3区
文献类型:
--
作者:
Marks MA;Kalaitzidou K;Gutekunst WR

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开发了一种用于合成树枝状-线性聚合物杂化物的模块化策略,所述聚合物杂化物由具有阳离子双MPA树枝状端基的柔性聚二甲基硅氧烷(PDMS)中间嵌段组成。本发明提供了一种可扩展的方法来获得季铵羧酸盐结构单元,并将其直接用于酯化化学,从而能够快速获得阳离子双-MPA树枝化基元。高度带电的树枝化基元与疏水性PDMS链端的会聚点击偶联给出了由不同树枝化基元代(G1-3)和季铵烷基链长度(C4、C8、C12、C16)组成的12元杂化物家族。这提供了具有可变疏水性、电荷密度和链端化合价的材料库。引入阳离子树枝化端基后,树枝化-线性PDMS杂化共聚物的物理行为发生了显着变化,并由于链的流动性受到抑制而导致软固体材料。这些PDMS-树枝化基元杂化物预期在本体交联有机硅系统中表现为表面活性抗微生物添加剂。聚合点击合成的PDMS-树枝状聚合物的混合物,以获得具有可调的链端化合价,电荷密度和疏水性的材料。开发了可扩展的季铵羧酸盐构建块,并且与PDMS中间块的连接导致硅氧烷链流动性和结晶度的显著变化。
A modular strategy for the synthesis of dendron-linear polymer hybrids comprised of a flexible polydimethylsiloxane (PDMS) midblock with cationic bis-MPA dendron end groups is developed. The invention of a scalable methodology to access quaternary ammonium carboxylate building blocks and their direct use in esterification chemistry enables rapid access to cationic bis-MPA dendrons. The convergent click coupling of highly charged dendrons to hydrophobic PDMS chain-ends gives a 12-membered family of hybrids that are comprised of different dendron generations (G1–3) and quaternary ammonium alkyl chain lengths (C4, C8, C12, C16). This provides a library of materials with variable hydrophobicity, charge density, and chain-end valency. The physical behavior of the dendron-linear PDMS hybrid copolymers significantly changes after introduction of the cationic dendron end-groups and leads to soft-solid materials as a result of inhibited chain mobility. These PDMS-dendron hybrids are expected to behave as surface-active antimicrobial additives in bulk cross-linked silicone systems. A convergent click synthesis of PDMS-dendrimer hybrids is described to give access to materials with tunable chain-end valency, charge density, and hydrophobicity. Scalable access to quaternary ammonium carboxylate building block is developed and attachment to a PDMS midblock leads to significant changes in the siloxane chain mobility and crystallinity.
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