一種聚陽離子季銨鹽高分子材料及其制備方法
【技術(shù)領(lǐng)域】
[0001]本發(fā)明屬于高分子材料技術(shù)領(lǐng)域,具體涉及一種聚陽離子季銨鹽高分子材料及其 制備方法。
【背景技術(shù)】
[0002] 隨著人類社會的快速發(fā)展和生活水平的不斷提高,越來越多的人發(fā)現(xiàn)微生物致病 菌已成為全世界范圍內(nèi)危害人類健康導(dǎo)致疾病甚至死亡的罪魁禍?zhǔn)譡1]。特別是近些年來 由于濫用抗生素而陸續(xù)出現(xiàn)耐藥性的超級細菌,更是導(dǎo)致了全球性的抗生素危機[2,3]。因 此,研發(fā)廣譜高效、持久可再生的新型抗菌劑顯得迫在眉睫。
[0003] 自從1915年此1如11^找從發(fā)現(xiàn)季銨鹽具有殺菌效果[4,5]后,季銨鹽類殺菌劑以 其低毒、廣譜及高效抗菌等優(yōu)異性能,已經(jīng)廣泛應(yīng)用于材料、化妝品、紡織、醫(yī)療及工業(yè)水處 理等領(lǐng)域。但是這些小分子抗菌劑性能不穩(wěn)定、易揮發(fā)及不易加工等缺點,同時易滲透擴散 引起毒性殘留[6],且如果長時間單一使用則易導(dǎo)致微生物致病菌的耐藥性[7]。相對而言, 聚陽離子季銨鹽類高分子材料性能穩(wěn)定,不易揮發(fā),而且抗菌活性長效耐久[8]。不僅如此, 聚陽離子季銨鹽類高分子材料比小分子季銨鹽有更好的抗菌活性,而且使用安全,不會滲 入人或動物表皮,選擇性高,使用壽命長、無殘留毒性等優(yōu)點[9,10],因而受到研究者們廣 泛的關(guān)注和開發(fā)。目前聚陽離子季銨鹽高分子材料主要有側(cè)鏈接有季銨鹽基團的聚丙烯酸 酯類高分子[11-13],側(cè)鏈接有季銨鹽基團的可降解聚酯高分子[14,15],主鏈含有季銨鹽 基團的高分子材料[16,17],以及通過季銨化修飾的天然高分子材料[18,19]等。綜合國內(nèi) 外文獻及專利,我們未發(fā)現(xiàn)有基于聚氧雜環(huán)丁烷的聚陽離子季銨鹽高分子材料報道。
[0004] 【參考文獻】 1. Fauci , A.S. ; Touchette,N.A. ; Folkers,G.K. Emerging infectious diseases: A l〇-year perspective from the National Institute of Allergy and Infectious Diseases. Emerg. Infect. Dis.2005, 11,519-525. 2. Burman, ff.J. Rip van winkle wakes up: Development of tuberculosis treatment in the 21st century. Clin. Infect. Dis. 2010, 50, 165-172. 3. Aziz, A.M. The role of healthcare strategies in controlling antibiotic resistance. Br. J. Nurs.2013, 22, 1066-1074. 4 . JACOBS ffA , HEIDELBERGER M. The quaternary salts of hexamethylenetetramine substituted benzyl halides and the hexamethylenetetrammoniums salts derived therefrom. J Biol Chem,1915,20: 659-683. 5. JACOBSWA, HEIDELBERGERM. The bactericidal properties of the quaternary salts of hexamethylenetetramine 11 . The problem of the chemotherapy ofexperimental bacterial infections. J Exp Med. 1916.23:63-568. 6. Mishra S,Karmodiya K, Parasuraman P,et al. Design, synthesis, and application of novel triclosan prodrugs as potential antimalarial and antibacterial agentsl. Bioorg Med Chem Lett, 2008, 16(10):5536. 7. J.C.Tiller, C. Sprich,L. Hartmann, Amphiphilic conetworks as regenerative controlled releasing antimicrobial coatings J. Controlled Re 1ease2005,103,355-367. 8. Majumdar, P.; Lee , E. ; Gubbins,N. ; Stafslien,S. J. ; Daniels , J.; Thorson,C.J. ; Chisholm ,B.J. Synthesis and antimicrobial activity of quaternary ammonium-functionalized POSS (Q-POSS) and polysiloxane coatings containing Q-POSS· Polymer2009,50,1124-1133· 9. Malmsten, M. Antimicrobial and antiviral hydrogels. Soft Matter2011, 7, 8725-8736. 10. Zheng,A.; Xue, Y.; Wei, D.; Li, S.; Xiao, H.; Guan,Y. Synthesis and characterization of antimicrobial polyvinyl pyrrolidone hydrogel as wound dressing. Soft Mater. 2014, 12, 179-187. 11. Dizman B, Elasri M.0, Mathias L.J; Synthesis and Antibacterial Activities of Water-Soluble Methacrylate Polymers Containing Quaternary Ammonium Compounds. J. Polym. Sci. Part A, Polym.Chem. 2006, 44, 5965-5973. 12. Palermo E. F,Kuroda K; Chemical Structure of Cationic Groups in Amphiphilic Polymethacrylates Modulates the Antimicrobial and Hemolytic Activities. Biomacromolecules. 2009,10,1416-1428. 13. Venkataraman, S.; Zhang, Y.; Liu, L. H.; Yang, Y. Y; Design, syntheses and evaluation of hemocompatible pegylated-antimicrobial polymers with well-controlled molecular structures. Biomaterials. 2010,31,1751-1756. 14. Riva, R.; Lussis, P.; Lenoir, S.; Jerome, C.; Jerome, R.; Lecomte, P. Contribution of "click chemistry',to the synthesis of antimicrobial aliphatic copolyester. Polymer. 2008, 49, 2023-2028. 15· Engler,.C.;Tan,J.P.K.;Ong,Z.Y·;Coady,D.J.;Ng,V.W.L.;Yang,Y.Y.; Hedrick,J.L. Antimicrobial polycarbonates : Investigating the impact of balancing charge and hydrophobicity using a same-centered polymer approach. Biomacromolecules2013,14,4331-4339. 16. Zheng, A.; Xu, X.; Xiao, H.; Guan,Y.; Li, S.; Wei, D. Preparation of antistatic and antimicrobial polyethylene by incorporating of comb-like ionenes. J. Mater. Sci. 2012, 47, 7201-7209. 17. Mattheis, C.; Zheng, M.; Agarwal, S. Closing one of the last gaps in polyionene compositions : Alkyloxyethylammonium ionenes as fast-acting biocides. Macromol. Biosci. 2012, 12, 341-349. 18. William Z. Xu, Guangzheng Gao,John F. Kadla; Synthesis of antibacterial cellulose materials using a ''clickable'' quaternary ammonium compound. Cellulose. 2013, 20:1187-1199. 19.程建華,胡勇有,李泗清;殼聚糖接枝聚季銨鹽的合成及調(diào)理性能,精細化工,2005, 22卷,2期。
【發(fā)明內(nèi)容】
[0005] 本發(fā)明的目的在于提供一種聚陽離子季銨鹽高分子材料的制備方法。
[0006] 本發(fā)明提供的一種聚陽離子季銨鹽高分子材料,所述材料結(jié)構(gòu)式為式(A)或式(B) 中任一種,
其中:R為氫、甲基或乙基中任一種,X為氯、溴或碘中任一種,m為3~6的整數(shù),η為1~4的 整數(shù),Ρ為6~18之間的奇數(shù),ζ為3或4。
[0007] 本發(fā)明提供的聚陽離子季銨鹽高分子材料的制備方法,其合成路線如下:
具體步驟是: 在惰性氣體條件下,將氧雜環(huán)丁烷類單體與催化劑及引發(fā)劑,在無水溶劑中發(fā)生聚合 反應(yīng),然后通過洗滌、干燥、減壓蒸餾除去溶劑進行精制提純得到聚合物前體;在惰性氣體 條件下,將所得聚合物前體與過量叔胺在無水溶劑中發(fā)生季銨化反應(yīng),再通過高真空度減 壓蒸餾除去溶劑和過量叔胺,則可得到聚陽離子季銨鹽高分子材料。
[0008] 所述氧雜環(huán)丁烷類單體為單體(1)和單體(2)組成的混合物,單體(1)的摩爾數(shù)占 單體(1)與單體(2)總摩爾數(shù)的0~100%。為方便稱謂,單體(1)表示為RXmOx,單體(2)表示為 REnOx;
其中:R為氫、甲基或乙基中任一種,(1)式中X為氯、溴或碘中任一種,m為3~6的整數(shù), (2)式中η為1~4的整數(shù)。
[0009] 本發(fā)明中,所述惰性氣體為高純氬氣(Ar)或高純氮氣(Ν2)中任一種。
[0010] 本發(fā)明中,所述催化劑為CF3S0