Inverse miniemulsion ATRP: A new method for synthesis and functionalization of well-defined water-soluble/cross-linked polymeric particles

Inverse miniemulsion ATRP: A new method for synthesis and functionalization of well-defined water-soluble/cross-linked polymeric particles
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DOI:
10.1021/ja060586a
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发表时间:
2006-04-26
影响因子:
15
通讯作者:
Matyjaszewski, K
Matyjaszewski, K
中科院分区:
化学1区
文献类型:
--
作者:
Oh, JK;Tang, CB;Matyjaszewski, K

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利用反相微乳液中水溶性单体的原子转移自由基聚合(ATRP),发展了一种新的纳米胶体粒子的合成和功能化方法,该方法由分子量分布窄、结构清晰的水溶性功能聚合物(M-w/M-nMn<1.3)组成。二硫键官能化交联剂的任选引入允许合成交联型(生物)可降解纳米凝胶。动态光散射(DLS)和原子力显微镜(AFM)测试表明,这些粒子具有良好的胶体稳定性。反相微乳液中的ATRP使材料具有几种理想的性能。胶体粒子保留了高度的卤素链端官能化,这使得进一步的官能化成为可能。制备了具有均匀交联型网络的交联型纳米凝胶。在还原环境中,它们被降解成相对分子质量分布较窄的单个聚合链(M-w/M-n<1.5)。更高的胶体稳定性、更高的溶胀率和更好的可控降解性表明,在反相微乳液中,ATRP制备的纳米凝胶优于传统的自由基聚合(RP)制备的纳米凝胶。
A new methodology for the synthesis and functionalization of nanometer-sized colloidal particles consisting of well-defined, water-soluble, functional polymers with narrow molecular weight distribution (M-w/M-n Mn < 1.3) was developed, utilizing atom transfer radical polymerization (ATRP) of water-soluble monomers in an inverse miniemulsion. The optional introduction of a disulfide-functionalized cross-linker allowed for the synthesis of cross-linked (bio)degradable nanogels. Dynamic light scattering (DLS) and atomic force microscopy (AFM) measurements indicated that these particles possessed excellent colloidal stability. ATRP in inverse miniemulsion led to materials with several desirable features. The colloidal particles preserved a high degree of halogen chain-end functionality, which enabled further functionalization. Cross-linked nanogels with a uniformly cross-linked network were prepared. They were degraded to individual polymeric chains with relatively narrow molecular weight distribution (M-w/M-n < 1.5) in a reducing environment. Higher colloidal stability, higher swelling ratios, and better controlled degradability indicated that the nanogels prepared by ATRP were superior to their corresponding counterparts prepared by conventional free radical polymerization (RP) in inverse miniemulsion.