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Poly(-caprolactone)-Poly(oxyethylene) Multiblock Copolymers Bearing Along the Chain Regularly Spaced Pendant Amino Groups

机译:沿链规则间隔的侧链氨基的聚(己内酯)-聚(氧乙烯)多嵌段共聚物

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摘要

Poly(-caprolactone) (PCL) macromers (M_n = 1.7-3.8 kDa) which contain one Z-protected NH2 group per chain were synthesized by ring-opening polymerization of -caprolactone in the presence of Sn(oct)2 using as initiator a diamine prepared by condensation of N-Boc-1,6-hexanediamine and N_α-Boc-N_e-Z-L-Lysine. The coupling of these macromers with COCl end-capped poly(oxyethylene) (PEO), M_n = 1.0 kDa, afforded amphiphilic multiblock poly(ether ester)s (PEEs) which have, along the chain, regularly spaced pendant protected amino groups. Deprotection, accomplished without chain degradation, yielded NH2 groups available for further reactions. The molecular structure of macromers and PEEs was investigated by 1H NMR and SEC. DSC and WAXS analyses showed that macromers and copolymers were semicrystalline and their Tm increased with increase in the molecular weight of PCL segments. The inherent viscosity values (0.25-0.30 dL ?nbsp;g-1), together with SEC analysis results, indicated moderate polymerization degrees.
机译:通过在Sn(oct)2的存在下,以己内酯为引发剂,对-己内酯进行开环聚合反应,合成每链含有一个Z-保护的NH2基团的聚己内酯(PCL)大分子单体(M_n = 1.7-3.8 kDa)。 N-Boc-1,6-己二胺和N_α-Boc-N_e-ZL-赖氨酸缩合制得的二胺。这些大分子单体与COCl封端的聚氧乙烯(PEO)(M_n = 1.0kDa)的偶联提供了两亲性的多嵌段聚(醚酯)(PEE),其沿链具有规则间隔的侧链保护的氨基。在没有链降解的情况下完成的脱保护,得到可用于进一步反应的NH 2基团。通过1 H NMR和SEC研究了大分子单体和PEE的分子结构。 DSC和WAXS分析表明,大分子单体和共聚物是半结晶的,并且它们的Tm随PCL链段分子量的增加而增加。固有粘度值(0.25-0.30dL·g-1)和SEC分析结果表明聚合度适中。

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