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常州大学材料科学与工程学院,常州,213164
纸质出版日期:2016-8-1,
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冯学鹏, 简鹏, 丁琳, 费俊豪, 盛扬, 张嵘. 基于聚丙交酯的光固化型可生物降解聚氨酯丙烯酸酯的合成和表征[J]. 高分子学报, 2016,(8):1062-1071.
Xue-peng Feng, Peng Jian, Lin Ding, Jun-hao Fei, Yang Sheng, Rong Zhang. Synthesis and Characterization of Biodegradable, Light-curing Polyurethane Acrylate Based on Polylactide[J]. Acta Polymerica Sinica, 2016,(8):1062-1071.
冯学鹏, 简鹏, 丁琳, 费俊豪, 盛扬, 张嵘. 基于聚丙交酯的光固化型可生物降解聚氨酯丙烯酸酯的合成和表征[J]. 高分子学报, 2016,(8):1062-1071. DOI: 10.11777/j.issn1000-3304.2016.15356.
Xue-peng Feng, Peng Jian, Lin Ding, Jun-hao Fei, Yang Sheng, Rong Zhang. Synthesis and Characterization of Biodegradable, Light-curing Polyurethane Acrylate Based on Polylactide[J]. Acta Polymerica Sinica, 2016,(8):1062-1071. DOI: 10.11777/j.issn1000-3304.2016.15356.
基于聚醚酯的聚氨酯丙烯酸酯具有应用于组织工程支架材料及相关生物医用材料的潜力,研究其可生物降解性及影响因素非常重要.聚醚酯是由PEG(Mw=400)引发L-丙交酯开环聚合而得到的PLLA-PEG-PLLA(PLEL)嵌段共聚物.它与二异氰酸酯(异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯)反应,并用甲基丙烯酸羟乙酯封端,得到聚氨酯丙烯酸酯低聚物,然后通过紫外固化得到聚氨酯丙烯酸酯材料(PUA).用NMR和GPC对PLEL二醇和预聚物进行了组成和分子量表征,用DSC和DMA对PUA进行了结构和物理性能表征以及用接触角、吸水率和质量分析方法对材料的亲水性和降解性能进行了表征.结果发现,随着PLLA疏水链段变长,PLEL软段分子量增大,材料的亲水性降低,交联度和降解速率变小.相同的软段,基于硬段HDI-HEMA的PUA材料比IPDI-HEMA的PUA有较低的Tg,较高的亲水性和降解速率.因为IPDI有环状结构,降低了PUA与水的相互作用.在3种不同降解条件下,氧化降解速率最高,酶解的速率高于水解.PUA材料的氧化降解速率取决于软段中PEG的含量,PLEL1000-HDI中PEG含量最高,其氧化降解最快,13周内失重率达到82.6%.
Polyurethane acrylate(PUA) based on polyether-ester have potential applications in tissue engineering
artificial scaffold
and other medical devices.Polyether ester diol triblock copolymers (PLLA-PEG-PLLA
PLEL) were synthesized by ring opening polymerization of L-lactide(L-LA) with the presence of polyethylene glycol (PEG).It is also used as soft segments for the preparation of polyurethane acrylate (PUA) oligomers containing PLEL-diol
diisocyanate (isophorone diisocyanate IPDI and hexamethylene diisocyanate HDI) and hydroxyethyl methacrylate (HEMA).PLEL-diols and PUA oligomers were characterized by 1H-NMR and GPC.The PUAs were fabricated under UV light
followed with structure and morphology analysis (DSC and DMA) and hydrophilic property characterization (contact angle and swelling).The results showed that increasing length of hydrophobic PLLA in PLEL-diols reduced PUA hydrophilicity
crosslink density and biodegradation rate.With the same soft segment
PUA made from hard segment of HDI-HEMA showed higher hydrophilicity and biodegradation rate than PUA based on IPDI-HEMA
because of a cyclic structure of IPDI reducing the interaction with water.The degradation experiment indicates that the PUA membranes degraded most rapidly in PBS/H2O2/CoCl2 solution
then slower in lipase solution
and lowest in pure PBS solution.The oxidative degradation rate of PUA materials depended on the content of PEG in the soft segment.The highest weight loss of 82.62% was recorded from the PLEL1000-HDI (the highest PED content in the PUA) degradation experiment in 13 weeks.
聚醚酯聚氨酯丙烯酸酯紫外光固化氧化降解酶解
Polyether esterPolyurethane acrylateUV-curingOxidative degradationEnzymatic degradation
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