血液相容性水性聚碳酸酯-聚醚聚氨酯的合成及其表徵研究

Abstract

本研究描述一種由軟鏈段和硬鏈段合成具有高固含量和低黏度的新型水性聚氨酯(WBPU)，在生物醫學領域有廣泛的應用潛力，軟鏈段由聚碳酸酯二醇(PC diol)和聚四亞甲基醚二醇(PTMO diol)組成，硬鏈段由 1,6-二異氰酸己二異氰酸酯(H12MDI)，以 2,2-二羥甲基丙酸 (DMPA)和2,2-二羥甲基丁酸(DMBA)分別作為鏈延長劑。為了在合成過程中提高乳液穩定性，我們使用非離子型表面活性劑，包括聚氧乙烯苯乙烯基苯酚醚和聚氧乙烯十三烷基醚。 調整軟硬鏈段的比例，由此可以改變水性聚氨酯的化學組成，再使用各種分析技術，如動態光散射儀(DLS)，了解水性聚氨酯粒徑分分布&表面電位、差示掃描量熱儀(DSC)、X 光繞射儀(XRD)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)、原子力顯微鏡(AFM)、衰減全反射紅外光譜儀(ATR-IR)、熱重分析儀(TGA)和接觸角測試儀(Contact angle)、動態機械分析儀(DMA)測量，來表現這些變化對水性聚氨酯玻璃轉移溫度、結晶程度、表面型態&表面粗糙度、官能基變化、熱變化及熱穩定性、親疏水性及應力-拉伸性能的影響。研究結果顯示，所製備的水性聚氨酯薄膜具有優良的機械性能，包括拉伸率 100% (10.8~22.6 MPa)、斷裂強度(11.7~30.9 MPa)和斷裂伸長率(173%~579%)。 軟鏈段聚碳酸酯二醇的比例提升，微相分離程度隨著增加，薄膜的水接觸角降低，從而增強了水性聚氨酯的親水性。我們挑選了兩種不同代表性的水性聚氨酯，分別為第二代及第三代生醫級PU，WBPU-B及WBPU-B3，這種新型水性聚氨酯配方在提升生物材料及血液接觸裝置的性能和耐久性方面具有顯著的潛力，該新型水性聚氨酯通過了血液相容性測試，溶血率均小於2%，符合材料溶血特性的評估標準(ASTM F756-17)。 整體而言，本研究開發的新型水性聚氨酯在生物醫學領域具有廣泛的應用前景。本研究調整化學組成後，成功地提升水性聚氨酯的機械性能和親水性，為未來的醫療器械和生物材料開發提供重要的參考。

This study describes the synthesis of a novel waterborne polyurethane (WBPU) with high solid content and low viscosity, composed of both soft and hard segments, and shows significant potential for biomedical applications. The soft segments consist of polycarbonate diol (PC diol) and polytetramethylene ether glycol (PTMO diol), while the hard segments are formed from 1,6-hexamethylene diisocyanate (H12MDI), with 2,2 Dimethylolpropionic acid (DMPA) and 2,2-Dimethylolbutanoic acid (DMBA) serving as chain extenders. To enhance emulsion stability during the synthesis, non-ionic surfactants, including polyoxyethylene styrenated phenyl and polyoxyethylene tridecyl ether. By adjusting the ratio of soft to hard segments, the chemical composition of the waterborne polyurethane (WBPU) can be modified. Various analytical techniques, such as dynamic light scattering (DLS) to analyze particle size distribution and surface zeta potential, differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-IR), thermogravimetric analysis (TGA), contact angle measurement, and dynamic mechanical analysis (DMA), were employed to evaluate how these changes affect the glass transition temperature, crystallinity, surface morphology and roughness, functional group variations, thermal behavior and stability, hydrophilicity/hydrophobicity, and stress-strain properties of the WBPU. The results show that the prepared WBPU films exhibit excellent mechanical properties, including tensile strength at 100% elongation (10.8–22.6 MPa), breaking strength (11.7–30.9 MPa), and elongation at break (173%–579%). As the proportion of polycarbonate diol in the soft segment increases, the degree of microphase separation also increases, resulting in a reduced water contact angle of the films and enhance hydrophilicity of the waterborne polyurethane (WBPU). We have selected two different representative types of waterborne polyurethanes, specifically the second generation and third-generation biomedical-grade PU, WBPU-B and WBPU-B3. This novel WBPU formulation demonstrates significant potential for improving the performance and durability of biomaterials and blood-contacting devices. The newly developed WBPU passed hemocompatibility tests, with hemolysis rates below 2%, in compliance with the evaluation standards for hemolytic properties of materials (ASTM F756-17). Overall, the novel WBPU developed in this study shows promising applications in the biomedical field. By adjusting its chemical composition, we successfully improved both the mechanical properties and hydrophilicity of the WBPU, providing a valuable reference for future development of medical devices and biomaterials.