Design And Synthesis Of Novel Multifunctional Perfluoroalkyl-Containing Textile Finishing Agents

Textiles are not only for cold-proof and prettification, but also be provided with multifunction of comfort and protection of personal safety along with the development of technology and improvement of people's living quality. Therefore, the requirement placed on novel and high performance textile finishing agents grows constantly. And the development of textile finishing agents with multifunction and multiplication is becoming the dominent trends in the future.In this dissertation, we designed and synthesized a series of multifunctional perfluoroalkyl-containing textile finishing agents expecting combine the water and oil repellency with antibacterial activity into a single molecule. It was described as follows.Part I: The diallyl group and perfluoroalkyl group were firstly introduced into one molecule to synthesis a multifunctional textile finishing agent capable of providing fabrics with barriers against bacterial, water and oil. We designed and synthesized four novel fluoroalkyl-containing analogues 3-6, and two known compounds 1 and 2 were synthesized as well in order to further investigate the structure relationship about these analogues and the influence of perfluoroalkyl group to their antimicrobial activities. Moreover, the introduction of diallyl groups into the molecule can not only enhance the antibacterial activity, but also extend their application fields which made itself a good monomer for homopolymerization or copolymerization with other monomer. The introduction of perfluoroalkyl group can endow the finishing fabric with water and oil repellent and increase the antibacterial activity to some extend. With all the designed quaternary ammonium compounds in hand, we examined their antibacterial activities. The perfluoroalkyl-containing quaternary ammonium salts 2-6 mainly exhibited excellent antibacterial activity against Gram-positive stain such as Staphylococuus aureus, the MIC (minimal inhibitory concertration) values were between 2.5-10μg/mL and the MBC (minimal bactericidal concentration) values were between 20-40μg/mL. They all showed weak activity against Gram-negative strain such as Escherichia coli, and against fungi such as Candida albicans, the MIC values and the MBC values were about 100μg/mL. Moreover, the relationship between their antibacterial activities and structures were further discussed.In preparation of quaternary ammonium salts antibacterial agent, we obtained PFDA copolymeric emulsion by one selected monomer through emulsion copolymerization, which was used to treat the cotton fabrics by the pad-dry-cure method. The treated fabrics showed good antibacterial properties. The inhibiting bacterial rates against E. coli 8099 and S. aureus ATCC 6538 were 99.9% and 92.4%, respectively. At the same time, the treated fabrics also showed good oil repellency but little waterproof property.Part II: Novel perfluoroalkyl-containing zinc pyrithione biocide 32 was designed and synthesized by introducing perfluoroalkyl-containing group into zinc pyrithione (ZPT) which was an excellent antibacterial agent. After attempting a lot of unsuccessful experiments, reaction of 4-methyl-pyridine with C₈F₁₇(CH₂)₃I in the presence of LDA followed by further oxidization of the resultant pyridine derivative 41 gave the pyridine N-oxide 44. Treatment of 44 with phosphorous oxychloride afforded the desirable chloride 47. Oxidization of compound 47 with H₂O₂ gave N-oxide 49. Reaction of 49 with NaSH provided the sulfide 40. Finally, treatment of compound 40 with NaOH/ZnSO₄ smoothly delivered perfluoroalkyl-containing zinc pyrithione antibacterial agent 32 in good yield. Part III: A peculiar class of pyridinium salts among cationic surfactants were prepared and their surface tension and antibacterial activities were examed, the property of quaternary ammonium salts 50,51,54 and 57 were compared. The surface tension of perfluoroalkyl-containing quaternary ammonium salts were extremely lower than that of non perfluoroalkyl-containing quaternary ammonium salts. The surface tension of compound 57 was about 10 mN / m lower than that of compound 54 while the difference of surface tension between compound 51 and compound 50 was just about 3 mN / m. All these quaternary ammonium salts mainly exhibited evident antibacterial activity for Gram-positive stain such as Staphylococcus aureus. Among them, the antibacterial activity of compound 57 was the best, and the MIC values were 12.5-50μg/mL, the MBC values were 50μg/mL. The antibacterial activities of compounds 50 and 51 containing both pyridium and triethylammonium were relatively weak.