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Structural analysis and degradation behavior in polyethylene glycol/poly(L‐lactide) copolymers

机译:聚乙二醇/聚L-丙交酯共聚物的结构分析和降解行为

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AbstractThe objective of this research is to investigate the molecular weight, degradation mechanism, and crystalline morphology of polyethylene glycol/poly(L‐lactide) (PEG/PLLA) copolymers during hydrolytic degradation. PEG/PLLA copolymers were prepared from cyclic L‐lactide and polyethylene glycol with molecular weights ranging from 1000 to 6000 Da. The structural analysis was carried out by GPC, DSC, FTIR,13C‐NMR, and1H‐NMR. Gel permeation chromatograms also indicate that the hydrolysis causes the change of mass distribution from a unimodal to a bimodal from. An exothermic recrystallization peak and its shoulder portion at the lower temperature range during melting appears immediately following the hydrolytic degradation. This indicates the heterogeneity of the crystals. The data of NMR and FTIR shows that during the initial period (0–200 h) of hydrolysis, there appears to be a formation of hydroxyl end groups connected to PEG blocks and carboxyl end groups connected to polylactide blocks. Due to the hydrophilic ethylene oxide segment in PEG/PLLA copolymers, the rate of hydrolysis is much faster during the first 200 h relative to longer hydrolysis time. It is therefore concluded that the chain scission during the initial period occurs at the ester linkage connecting PEG and PLLA blocks, in addition to ester groups within the PLLA blocks. © 1994 John Wiley
机译:摘要 研究聚乙二醇/聚L-丙交酯(PEG/PLLA)共聚物在水解降解过程中的分子量、降解机理和结晶形貌。以环状L-丙交酯和聚乙二醇为原料制备了PEG/PLLA共聚物,分子量范围为1000-6000 Da。采用GPC、DSC、FTIR、13C‐NMR和1H‐NMR进行结构分析。凝胶渗透色谱图还表明,水解导致质量分布从单峰变为双峰。在熔融过程中,在较低温度范围内立即出现放热再结晶峰及其肩部,水解降解后立即出现。这表明晶体的非均质性。NMR和FTIR的数据显示,在水解的初始阶段(0-200小时),似乎形成了连接到PEG嵌段的羟基末端基团和连接到聚丙交酯嵌段的羧基末端基团。由于PEG/PLLA共聚物中的亲水环氧乙烷片段,相对于较长的水解时间,前200 h的水解速率要快得多。因此,得出结论,除了PLLA块内的酯基外,初始期的链断裂还发生在连接PEG和PLLA块的酯键处。© 1994 约翰·威利

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