Complex, Degradable Polyester Materials via Ketoxime Ether-Based Functionalization: Amphiphilic, Multifunctional Graft Copolymers and Their Resulting Solution-State Aggregates
Complex, Degradable Polyester Materials via Ketoxime Ether-Based Functionalization: Amphiphilic, Multifunctional Graft Copolymers and Their Resulting Solution-State Aggregates
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DOI：
10.1002/pola.24132
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发表时间：
2010-08-15
影响因子：
--
通讯作者：
Wooley, Karen L.
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文献类型：
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作者：
Iha, Rhiannon K.;Van Horn, Brooke A.;Wooley, Karen L.
利用统计共聚物(poly(epsilon-caprolactone)-graft-poly(ethylene-co-poly(epsilon-caprolactone)-co-(2-oxepane-1，5-dione)，)主链上的酮，通过接枝策略合成了可降解的两亲性接枝共聚物PCL-g-PEO。通过形成稳定的酮肟醚键，3 kDa PEO接枝和对甲氧基苄基侧链以高度的保真度和效率被引入到聚酯的主链上，核磁共振光谱和凝胶渗透色谱分析证实了这一点(某些情况下接枝效率为90%)。所得嵌段接枝共聚物与母体PCL和PEO聚合物相比，表现出显著的热差异，特别是观察到的熔融转变温度T-m降低。通过透射电子显微镜和原子力显微镜观察到，P(CL-co-OPD-co-(OPD-g-PEO))聚合物在水溶液中自组装形成球形胶束，P(CL-co-OPD-co-(OPD-g-PEO)-co-(OPD-g-pMeOBn))形成圆柱状或棒状胶束。(C)2010年威利期刊公司J Polym Sci Part A：Polym Chem 48：3553-3563,2010
Degradable, amphiphilic graft copolymers of poly(epsilon-caprolactone)-graft-poly(ethylene oxide), PCL-g-PEO, were synthesized via a grafting onto strategy taking advantage of the ketones presented along the backbone of the statistical copolymer poly(epsilon-caprolactone)-co-(2-oxepane-1,5-dione), (PCL-co-OPD). Through the formation of stable ketoxime ether linkages, 3 kDa PEO grafts and p-methoxybenzyl side chains were incorporated onto the polyester backbone with a high degree of fidelity and efficiency, as verified by NMR spectroscopies and GPC analysis (90% grafting efficiency in some cases). The resulting block graft copolymers displayed significant thermal differences, specifically a depression in the observed melting transition temperature, T-m, in comparison with the parent PCL and PEO polymers. These amphiphilic block graft copolymers undergo self-assembly in aqueous solution with the P(CL-co-OPD-co-(OPD-g-PEO)) polymer forming spherical micelles and a P(CL-co-OPD-co-(OPD-g-PEO)-co-(OPD-g-pMeOBn)) forming cylindrical or rod-like micelles, as observed by transmission electron microscopy and atomic force microscopy. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3553-3563, 2010