Antithrombogenic poly(2-methoxyethyl acrylate) elastomer via triblock copolymerization with poly(methyl methacrylate)
Antithrombogenic poly(2-methoxyethyl acrylate) elastomer via triblock copolymerization with poly(methyl methacrylate)
复制标题
DOI：
10.1016/j.polymer.2021.123876
复制
发表时间：
2021-05-30
期刊：
影响因子：
4.6
通讯作者：
Hotta, Atsushi
中科院分区：
文献类型：
--
作者：
Kurokawa, Naruki;Endo, Fuyuaki;Hotta, Atsushi
对于血液接触生物医学器械的开发，通过抗血栓表面防止血小板粘附并避免随后的血栓形成至关重要。聚（丙烯酸2-甲氧基乙酯）（PMEA）是一种具有优异抗血栓形成性能的合成粘性聚合物，已被用作生物医学用途的抗血栓形成涂层。然而，由于PMEA的玻璃化转变温度(Tg)为-25℃，因此PMEA涂层由于其类液体的特性而很容易破裂。因此，迫切需要固化PMEA以提高PMEA涂层的稳定性。此外，一旦固化，PMEA不仅可以用于涂层，还可以用于医疗器械的结构材料，扩大了PMEA的应用范围。本研究首先将PMEA与聚甲基丙烯酸甲酯(PMMA)进行三嵌段共聚固化，得到具有优异抗血栓形成能力的热塑性弹性体。我们通过原子转移自由基聚合（ATRP）合成了具有不同体积分数的PMMA（fMMA）的PMMA-PMEA-PMMA三嵌段共聚物。通过质子核磁共振（1H NMR）分析和凝胶渗透色谱（GPC）对新型三嵌段共聚物的合成和化学结构进行了表征和证实。然后将合成的弹性体三嵌段在180℃下压塑以获得固体透明薄膜。测量了拉伸性能，通过改变 fMMA 可以清楚地观察到从软弹性体相到硬塑性相的剧烈变化。之前的研究发现，新型三嵌段体比其他固化 PMEA 具有显着更高的拉伸强度。血小板粘附测试显示，fMMA为0.12和0.40的三嵌段体上粘附的血小板数量与纯PMEA几乎相同，表明合成的三嵌段体具有与液体PMEA相似的优异的抗血栓形成能力。对水合水和微相分离结构的进一步研究最终表明，具有足够量的中间水或表面具有微相分离的新型三嵌段共聚物具有优异的抗血栓形成性。
For the development of blood-contacting biomedical devices, preventing platelet adhesion and avoiding subsequent thrombosis through antithrombogenic surface are vitally important. Poly (2-methoxyethyl acrylate) (PMEA) is a synthetic viscous polymer with an excellent antithrombogenic property, which has already been used as an antithrombogenic coating for biomedical purposes. The PMEA coating, however, can be easily broken due to its liquid-like feature, since the glass transition temperature (Tg) of PMEA is at - 25 omicron C. Solidifying PMEA has, therefore, been desperately desired for the improvement of the stability of PMEA coating. Also, once solidified, PMEA could be utilized not only for coating but also for structural materials for medical devices, expanding the application range of PMEA. In this study, PMEA was first solidified by triblock copolymerization with poly (methyl methacrylate) (PMMA) to obtain thermoplastic elastomers with excellent antithrombogenicity. We synthesized PMMA-PMEA-PMMA triblock copolymers with different volume fractions of PMMA (fMMA) by atom transfer radical polymerization (ATRP). The synthesis and the chemical structures of the new triblock copolymers were characterized and confirmed by proton nuclear magnetic resonance (1H NMR) analyses and gel permeation chromatography (GPC). The synthesized elastomeric triblocks were then compressionmolded at 180 omicron C to obtain solid transparent films. The tensile property was measured and the drastic change from the soft-elastomer phase to the hard-plastic phase was clearly observed by varying fMMA. It was found that the new triblocks possessed significantly higher tensile strengths than the other solidified PMEA by the previous studies. The platelet adhesion test revealed that the number of adherent platelets on the triblocks with fMMA of 0.12 and 0.40 was almost the same as that on pure PMEA, indicating that the synthesized triblocks possessed excellent antithrombogenicity similar to liquid PMEA. Further investigation on hydrated water and microphaseseparated structures eventually revealed that the new triblock copolymers with a sufficient amount of intermediate water or with microphase separation on the surface resulted in excellent antithrombogenicity.