Copolymers from Unsaturated Macrolactones: Toward the Design of Cross-Linked Biodegradable Polyesters

Copolymers from Unsaturated Macrolactones: Toward the Design of Cross-Linked Biodegradable Polyesters
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DOI:
10.1021/bm200084y
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发表时间:
2011-03-01
期刊:
影响因子:
6.2
通讯作者:
Heise, Andreas
Heise, Andreas
中科院分区:
化学2区
文献类型:
--
作者:
van der Meulen, Inge;Li, Yingyuan;Heise, Andreas

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研究了不饱和丙烯酸内酯globalide和ambrettlastine与1,5-二氧杂环庚烷-2-酮(DXO)和4-甲基己内酯(4 MeCL)的开环聚合反应,合成了一系列无规共聚酯。C-13 NMR二联体分析证实了共聚物的无规性,而与共聚单体比率无关。热分析表明,与大环内酯均聚物相比,加入共聚单体可降低聚合物的熔点。降低取决于共聚单体比率。使用过氧化二异丙苯,这导致在完全无定形的不溶性网络的不饱和共聚物进行热交联。发现掺入10%的不饱和macolactone足以获得95wt%的凝胶含量。初步降解试验证实,交联共聚物是酶促降解的,并且亲水性共聚单体如DXO的掺入增强了降解。
The enzymatic synthesis of a series of random copolyesters by ring-opening polymerization of unsaturated rnacrolactones like globalide and ambrettolide with 1,5-dioxepan-2-one (DXO) and 4-methyl caprolactone (4MeCL) was investigated. C-13 NMR diad analysis confirmed the randomness of copolymers irrespective of the comonomer ratios. Thermal investigation showed that incorporating the comonomers lowered the melting points of the polymers as compared with the macrolactone homopolymers. The decrease was dependent on the comonomer ratio. The unsaturated copolymers were thermally cross-linked using dicumyl peroxide, which resulted in completely amorphous insoluble networks. It was found that 10% incorporation of the unsaturated macolactone was sufficient to obtain a gel content of 95 wt %. Preliminary degradation tests confirm that the cross-linked copolymers are enzymatically degradable and that the incorporation of hydrophilic comonomers like DXO enhances degradation.