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基于聚(3-羟基丁酸酯-co-3-羟基己酸酯)和聚乙二醇通过熔融聚合制备可生物降解弹性体聚(醚-酯聚氨酯)的合成、表征及生物相容性

Synthesis, characterization and biocompatibility of biodegradable elastomeric poly(ether-ester urethane)s Based on Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and Poly(ethylene glycol) via melting polymerization.

作者信息

Li Zibiao, Yang Xiaodi, Wu Linping, Chen Zhifei, Lin Yuting, Xu Kaitian, Chen Guo-Qiang

机构信息

Multidisciplinary Research Center, Shantou University, Shantou, Guangdong 515063, PR China.

出版信息

J Biomater Sci Polym Ed. 2009;20(9):1179-202. doi: 10.1163/156856209X452944.

Abstract

Poly(ether-ester urethane)s (PUs) multiblock co-polymers were synthesized from telechelic hydroxylated poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and poly(ethylene glycol) (PEG) via a melting polymerization (MP) process using 1,6-hexamethylene diisocyanate (HDI) as a non-toxic coupling agent for the first time. The PHBHHx segments and PEG segments in the multiblock co-polymers behaved as a hard, hydrophobic and a soft, hydrophilic part, respectively. Their chemical structures and molecular characteristics were studied by gel-permeation chromatography (GPC), (1)H-NMR and Fourier transform infrared spectroscopy (FT-IR). The PU produced via the MP method showed a higher molecular weight than those resulting from the solvent polymerization (SP) reported previously. Thermal properties showed enhanced thermal stability with semi-crystalline morphology via incorporation of PEG. The segments compositions evaluated from thermogravimetric analysis (TGA) two-step thermal decomposition profiles suggested that MP enhanced the reactivity of PEG compared with the SP process. It was in good agreement with those calculated from (1)H-NMR, as well as the precursor feed ratio, respectively. Water contact angle measurements revealed that surface hydrophilicity of the PUs was enhanced by incorporating the PEG segment into PHBHHx polymer backbone. The mechanical properties assessment of the PUs recorded an improved and adjustable ductility and toughness than pure PHBHHx while preserving the tensile strength. Samples synthesized via MP were resistant to hydrolytic and lipase degradation, yet the multiblock co-polymers incorporating the highest amount of PEG degraded at the highest rate. SEM studies revealed that the surface of the PU films became increasingly porous as the degradation proceeded. Implantation of PU in mouse abdominal cavity indicated that tissue regeneration and tissue compatibility of PU film was better than that of PHBHHx-only film.

摘要

首次通过熔融聚合(MP)工艺,以1,6 - 六亚甲基二异氰酸酯(HDI)作为无毒偶联剂,由遥爪羟基化聚(3 - 羟基丁酸酯 - co - 3 - 羟基己酸酯)(PHBHHx)和聚乙二醇(PEG)合成了聚(醚 - 酯聚氨酯)(PU)多嵌段共聚物。多嵌段共聚物中的PHBHHx链段和PEG链段分别表现为硬的、疏水部分和软的、亲水部分。通过凝胶渗透色谱(GPC)、¹H - NMR和傅里叶变换红外光谱(FT - IR)研究了它们的化学结构和分子特征。通过MP方法制备的PU显示出比先前报道的溶剂聚合(SP)方法制备的PU更高的分子量。热性能表明,通过引入PEG,热稳定性增强,具有半结晶形态。从热重分析(TGA)两步热分解曲线评估的链段组成表明,与SP工艺相比,MP增强了PEG的反应性。这与分别从¹H - NMR计算得到的结果以及前体进料比非常吻合。水接触角测量表明,通过将PEG链段引入PHBHHx聚合物主链中,PU的表面亲水性得到增强。PU的力学性能评估记录显示,与纯PHBHHx相比,其延展性和韧性得到改善且可调节,同时保持了拉伸强度。通过MP合成的样品对水解和脂肪酶降解具有抗性,但含有最高量PEG的多嵌段共聚物降解速率最高。扫描电子显微镜(SEM)研究表明,随着降解的进行,PU膜的表面变得越来越多孔。将PU植入小鼠腹腔表明,PU膜的组织再生和组织相容性优于仅含PHBHHx的膜。

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