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Effect of Hydroxyapatite Nanoparticles on the Degradability of Random Poly(butylene terephthalate- co -aliphatic dicarboxylate)s Having a High Content of Terephthalic Units

机译:羟基磷灰石纳米颗粒对高对苯二甲酸单元含量的无规聚对苯二甲酸丁二醇酯-共脂族二羧酸酯的降解性的影响

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摘要

Copolyesters derived from 1,4-butanediol and constituted also of aliphatic and aromatic dicarboxylate units in a molar ratio of 3:7 were synthesized by a two-step polycondensation procedure. Succinic, adipic, and sebacic acids were specifically selected as the aliphatic component whereas terephthalic acid was chosen as the aromatic moiety. The second synthesis step was a thermal transesterification between the corresponding homopolymers, always attaining a random distribution as verified by NMR spectroscopy. Hybrid polymer composites containing 2.5 wt % of hydroxyapatite (HAp) were also prepared by in situ polymerization. Hydroxyl groups on the nanoparticle surface allowed the grafting of polymer chains in such a way that composites were mostly insoluble in the typical solvents of the parent copolyesters. HAp had some influence on crystallization from the melt, thermal stability, and mechanical properties. HAp also improved the biocompatibility of samples due to the presence of Ca 2+ cations and the damping effect of phosphate groups. Interestingly, HAp resulted in a significant increase in the hydrophilicity of samples, which considerably affected both enzymatic and hydrolytic degradability. Slight differences were also found in the function of the dicarboxylic component, as the lowest degradation rates was found for the sample constituted of the most hydrophobic sebacic acid units.
机译:通过两步缩聚法合成了由1,4-丁二醇衍生并还由脂族和芳族二羧酸酯单元以3:7的摩尔比组成的共聚酯。特别选择琥珀酸,己二酸和癸二酸作为脂肪族组分,而选择对苯二甲酸作为芳族部分。第二个合成步骤是在相应的均聚物之间进行热酯交换,始终获得随机分布,这已通过NMR光谱证实。还通过原位聚合制备了包含2.5重量%的羟基磷灰石(HAp)的杂化聚合物复合材料。纳米颗粒表面上的羟基以这种方式接枝聚合物链,使得复合材料大部分不溶于母体共聚酯的典型溶剂中。 HAp对熔体的结晶,热稳定性和机械性能有一定影响。由于Ca 2+阳离子的存在和磷酸根基团的阻尼作用,HAp还改善了样品的生物相容性。有趣的是,HAp导致样品的亲水性显着增加,这大大影响了酶促降解和水解降解能力。在二羧酸组分的功能上也发现了细微的差异,因为发现由最疏水的癸二酸单元组成的样品的最低降解速率。

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