基于双全氟支化醚链的高环境安全性氟碳表面活性剂的设计合成及其构效关系研究

Considering that traditional fluorinated surfactants with C8 and C6 perfluorinated straight-chain are difficult to degrade, while fluorinated surfactants with single C6 perfluorinated branched chain has no obvious persistence bioaccumulation, but their surface properties are difficult to reach those of C8 perfluorinated chain, this project intends to study the environmental safety and surface properties of fluorinated surfactants based on double C6 perfluorinated branched ether chain. Fluorinated surfactants with perfluoro-2-methyl-2-pentane ether chain are designed from HFPD (perfluoro-2-methyl-2-pentene) and divinylsulfonamides, toxicity prediction is carried out to clarify the relationship between structure and toxicity. Then, we will synthesis of fluorinated surfactants, and focus on the enhancement of surface properties based on the two-tailed structure, and quantify the structure to improve the surface property. Meanwhile, the influence of oxygen atoms in perfluorinated ether chain on degradation is investigated, the toxicity of the newly synthesized surfactants is tested, and then the environmental safety is evaluated. Finally, the structure-activity relationships between high-efficiency fluorinated surfactants and linking chains and hydrophilic groups are revealed, design and synthesis of environmentally-friendly and high-efficiency fluorinated surfactants are optimized to solve the contradiction between environmental friendliness and high efficiency. The present research will enrich the research fields of fluorinated surfactants and provide theoretical support for the development of low-cost and efficient fluorinated surfactants.

本项目针对传统直链型全氟C8和C6链段氟碳表面活性剂难降解，而单支链化的全氟C6链段无明显持久生物蓄积性但其表面性能难达到全氟C8链段的问题，拟开展基于双支链化的全氟C6醚链对氟碳表面活性剂的环境安全性及表面性能增效的基础研究。以六氟丙烯二聚体和双乙烯磺酰胺类化合物为原料设计含双全氟-2-甲基-2-戊醚链结构的氟碳表面活性剂并进行毒性预测研究，明晰结构与毒性的关系。进而合成氟碳表面活性剂，探索双尾结构对表面性能的增强效果，量化结构对性能的提升。同时，考察全氟醚链中的氧原子对降解性的影响，开展表面活性剂分子的毒理性测试，并进行环境安全性评价。最后，从结构与性能的关系出发，揭示高效氟碳表面活性剂和连接链、亲水基的构效关系，反演优化环保高效型氟碳表面活性剂的设计及合成，解决氟碳表面活性剂环保与高效的矛盾问题。研究成果将丰富氟碳表面活性剂的研发领域，为价廉高效氟碳表面活性剂的开发提供理论支撑。

消防用的氟碳表面活性剂全氟辛基磺酰氟衍生物（通称为PFOS）因环境危害被联合国斯德哥尔摩公约列为了持久性污染物而被全世界所禁止。而目前开发出的C4氟碳链产品其部分性能无法达到长链PFOS/PFOA的功效，完全依赖进口性能较优的直链C6氟碳链段同样存在污染生态环境和危害人体健康的风险，安全环保且价廉高效的PFOS/PFOA类替代品的研发，已成为紧迫的氟化工精细化学品研究问题之一。项目针对传统直链型全氟C8和C6链段氟碳表面活性剂难降解，而单支链化的全氟C6链段无明显持久生物蓄积性但其表面性能难达到全氟C8链段的问题，以全国产化的六氟丙烯多聚体为廉价原料设计合成了环境安全的含全氟-2-甲基-2-戊醚链结构的氟碳表面活性剂，并进行了毒性预测研究，明晰了结构与毒性的关系。并从结构与性能的关系出发，揭示了高效氟碳表面活性剂和连接链、亲水基的构效关系，反演优化环保高效型氟碳表面活性剂的设计及合成，解决了氟碳表面活性剂环保与高效的矛盾问题。研究成果丰富了氟碳表面活性剂的研发领域，为价廉高效氟碳表面活性剂的开发提供理论支撑。项目组依托课题所制备的4类氟碳表面活性剂及其协同增效复配体系，开发了4种满足国家标准的水成膜泡沫灭火剂并完成了中试，初步具备了产业应用的潜能，目前正在进行商业对接。项目研制过程中在国际国内高水平期刊上发表论文6篇，成功受理国家发明专利7项（授权2项）。项目负责人获得第一届全国创新创业优秀博士后、江苏省创新创业优秀博士后，依托项目获得第一届全国博士后创新创业大赛总决赛银奖和“科创江苏”创新创业大赛新材料创新组总决赛一等奖（第一），入选江苏省“333”第三层次。项目培养了2名研究生，所指导的研究生依托项目获得第十二届“挑战杯”江苏省大学生创业计划竞赛金奖。