聚苯硫醚 (PPS) 广泛用于汽车零部件、机械零件、电气配件和防腐涂料,但其疏水性限制了其在生物材料、医疗设备、电池隔膜和油污分离膜中的应用。为了提高 PPS 的亲水性,硝酸氧锆与 3,5-二氯水杨酸 (SA) 反应生成羧酸锆 (ZrSA)。然后,ZrSA 通过共聚掺入 PPS 的主链中,得到亲水性共聚物 (ZrSA-PPS)。同时,SA 共聚到 PPS 的主链中,生产 SA-PPS。接下来,将 SA-PPS 和 ZrO2 物理共混得到亲水性复合材料 (ZrO2/SA-PPS)。ZrSA-PPS 的熔点范围为 278.19 至 281.16 °C,略高于 ZrO2/SA-PPS 的熔点 (278.39–279.95 °C),但其结晶度 (34.3–41.2 %) 低于 ZrO2/SA-PPS 的熔点 (42.2–51.6 %)。ZrSA-PPS 和 ZrO2/SA-PPS 的最高分解温度升高了约 10 °C,表明 Zr-O 键阻碍了分子链的热诱导运动。ZrSA-PPS 的拉伸强度为 40.8-70.5 MPa,弯曲强度为 46.4-103.4 MPa。ZrO2/SA-PPS 的拉伸和弯曲强度(14.6-65.1 Mpa 和 23.1-100.3 Mpa)明显低于 ZrSA-PPS。这表明 ZrSA 交联结构可以防止裂纹扩展。ZrSA-PPS 和 ZrO2/SA-PPS 的水接触角范围分别为 59.0° 至 76.5° 和 61.6°–78.5° (Neat-PPS, ∼87.9°)。ZrO2 的团聚导致 ZrO2/SA-PPS 的水接触角略高于 ZrSA-PPS。 ZrSA-PPS 增强的亲水性得益于大链间距、强极性基团和氢键的形成。我们的研究可能会阐明 PPS 的亲水改性,这应该为 PPS 在亲水应用中提供有价值的指导和选择。
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Hydrophilicity modification of polyphenylene sulfide: A comparative study on the introduction of Zr by physical blending and copolymerization
Polyphenylene sulfide (PPS) is widely used in auto components, machinery parts, electrical accessories, and anti-corrosion coatings, but its hydrophobicity restricts its application in biomaterials, medical equipment, battery separators, and oil pollution separation membranes. To improve the hydrophilicity of PPS, zirconium oxynitrate reacted with 3,5-dichlorosalicylic acid (SA) to generate zirconium-carboxylate (ZrSA). ZrSA was then incorporated into the main chain of PPS through copolymerization to yield hydrophilic copolymers (ZrSA-PPS). Meanwhile, SA was copolymerized into the main chain of the PPS to produce SA-PPS. Next, SA-PPS and ZrO2 were physically blended to obtain hydrophilic composites (ZrO2/SA-PPS). The melting point of ZrSA-PPS ranged from 278.19 to 281.16 °C, which was slightly higher than that of ZrO2/SA-PPS (278.39–279.95 °C), but its crystallinity (34.3–41.2 %) was lower than that of ZrO2/SA-PPS (42.2–51.6 %). The maximum decomposition temperatures of ZrSA-PPS and ZrO2/SA-PPS were increased by about 10 °C, indicating that the Zr–O bonds obstruct the thermally induced movements of the molecular chain. The ZrSA-PPS possessed a tensile strength of 40.8–70.5 MPa and a flexural strength of 46.4–103.4 MPa. The tensile and flexural strengths of ZrO2/SA-PPS (14.6–65.1 Mpa and 23.1–100.3 Mpa) were significantly inferior to that of ZrSA-PPS. This revealed that the ZrSA cross-linked structure can prevent crack propagation. The water contact angle of ZrSA-PPS and ZrO2/SA-PPS were ranged from 59.0° to 76.5° and 61.6°–78.5° (Neat-PPS, ∼87.9°), respectively. The agglomeration of ZrO2 resulted in a slightly higher water contact angle for ZrO2/SA-PPS than for ZrSA-PPS. The enhanced hydrophilicity of ZrSA-PPS benefited from the formation of large chain spacing, strong polar groups, and hydrogen bonds. Our study may shed light on the hydrophilic modification of PPS, which should offer a valuable guide and option for PPS in hydrophilic applications.